KR20120009721A - Positive photoresist composition - Google Patents
Positive photoresist composition Download PDFInfo
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- KR20120009721A KR20120009721A KR1020100070173A KR20100070173A KR20120009721A KR 20120009721 A KR20120009721 A KR 20120009721A KR 1020100070173 A KR1020100070173 A KR 1020100070173A KR 20100070173 A KR20100070173 A KR 20100070173A KR 20120009721 A KR20120009721 A KR 20120009721A
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- photoresist composition
- positive photoresist
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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
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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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
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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
- G03F7/0397—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 an alicyclic moiety in a side chain
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- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
본 발명은 포지티브 포토레지스트 조성물에 관한 것이다.The present invention relates to a positive photoresist composition.
최근, 집적회로의 집적도가 증가함에 따라, 플루오르화 크립톤(이하, KrF라 한다), 플루오르화 아르곤(이하, ArF라 한다) 등의 엑시머 레이저를 이용하는 포토리소그래피가 주를 이루고 있다. 이러한 포토리소그래피에서 산 촉매 및 화학증폭 효과를 이용한, 소위 말하는 화학증폭형 레지스트가 채택된다. 화학증폭형 레지스트가 사용되는 경우, 방사선의 조사부에서는 광산발생제로부터 발생한 산이 열처리에 의하여 확산되고, 확산된 산을 촉매로써 사용하는 반응에 의해 조사부의 알칼리 현상액에 대한 용해성이 변화되어 포지티브 타입 또는 네가티브 타입 패턴이 수득된다.In recent years, as the degree of integration of integrated circuits has increased, photolithography using excimer lasers, such as krypton fluoride (hereinafter referred to as KrF) and argon fluoride (hereinafter referred to as ArF), has become a major factor. In such photolithography, so-called chemically amplified resists using an acid catalyst and a chemical amplification effect are adopted. When a chemically amplified resist is used, the acid generated from the photoacid generator is diffused by heat treatment in the radiation irradiator, and the solubility in the alkaline developer of the irradiated portion is changed by a reaction using the diffused acid as a catalyst. A type pattern is obtained.
또한, 집적도의 증가에 따라 포토레지스트의 조성물의 주성분이 변화되었는데 일반적으로 g, i-line에서는 노볼락 페놀계 및 나프토디아조계가 주성분으로, KrF 엑시머 레이저에서는 페놀성 히드록시와 광산발생제가 주성분으로, ArF의 엑시머 레이저에서는 아크릴레이트 계열의 레진과 광산 발생제가 주성분으로 사용되고 있다. 이러한 변화는 주성분의 극성이 점점 높아지게 변화된 것으로, 적절한 유기용매를 사용하지 않으면 용해도가 저하되며, 저장시에 재석출되어 파티클 결함이 야기되며 또한 포토레지스트를 도포할 경우 공정결함으로 나타나게 된다.In addition, the main component of the composition of the photoresist was changed with the increase of the density. In general, novolak phenol and naphthodiazo-based components were the main components in g and i-line, and phenolic hydroxy and photoacid generator were the main components in KrF excimer laser. In the excimer laser of ArF, acrylate resin and photoacid generator are used as main components. This change is the polarity of the main component is gradually increased, the solubility is lowered without the use of an appropriate organic solvent, re-precipitated upon storage, causing particle defects, and also appear to be a process defect when the photoresist is applied.
본 발명은 용해성이 향상되고, 온도가 변화하는 환경에서도 저장안정성이 우수한 포지티브 포토레지스트 조성물을 제공하는 것이다.The present invention provides a positive photoresist composition having improved solubility and excellent storage stability even in an environment where temperature changes.
또한, 본 발명의 목적은 인체에 무해하고, 환경친화적인 포지티브 포토레지스트 조성물을 제공하는 것이다.It is also an object of the present invention to provide a positive photoresist composition that is harmless to the human body and is environmentally friendly.
본 발명은 (a) 알칼리 가용성 수지; (b) 감광성 화합물; 및 (c) 하기 화학식 1로 표시되는 화합물과 유기용매를 포함하는 용매를 포함하는 것을 특징으로 하는 포지티브 포토레지스트 조성물을 제공한다.The present invention (a) alkali soluble resin; (b) photosensitive compounds; And (c) provides a positive photoresist composition comprising a solvent comprising a compound represented by the formula (1) and an organic solvent.
<화학식 1><Formula 1>
본 발명의 포지티브 포토레지스트 조성물은 용해성이 향상되고, 온도가 변화하는 환경에서도 재석출이 발생하지 않아 장기보존이 가능하다. 또한 본 발명의 포지티브 포토레지스트 조성물은 현상 이물질이 기판 상에 도포 또는 재흡착을 저지할 수 있어, 현상결함이 없는 우수한 프로파일을 형성할 수 있다.The positive photoresist composition of the present invention improves solubility and does not cause reprecipitation even in an environment where temperature changes, and thus long-term storage is possible. In addition, the positive photoresist composition of the present invention may prevent the development foreign matter from being applied or resorbed on the substrate, thereby forming an excellent profile without developing defects.
이하, 본 발명에 대하여 상세히 설명하다.Hereinafter, the present invention will be described in detail.
본 발명의 포지티브 포토레지스트 조성물은, (a) 알칼리 가용성 수지, (b) 감광성 화합물 및 (c) 용매를 포함한다.The positive photoresist composition of this invention contains (a) alkali-soluble resin, (b) photosensitive compound, and (c) solvent.
본 발명의 포지티브 포토레지스트 조성물에 포함되는 (a) 알칼리 가용성 수지는 노볼락계 수지, 폴리비닐알콜, 폴리비닐알킬에테르, 스티렌과 아크릴산의 공중합체, 메타크릴산과 메타크릴산 알킬에스테르와의 공중합체, 히드록시스티렌의 중합체, 폴리비닐히드록시벤조에이트 및 폴리비닐히드록시벤젠으로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다. 여기서, 상기 (a) 알칼리 가용성 수지는 노볼락계 수지를 이용하는 것이 바람직하다. 상기 노볼락계 수지는, 방향족 알코올인 페놀, 메타크레졸, 파라크레졸 또는 이들의 혼합물과 포름알데히드를 반응시켜 합성한 중합체이다. 또한, 포토레지스트의 성능 개선을 위하여 상기 노볼락계 수지 중에서 고분자, 중분자 또는 저분자 등을 제거하여 용도에 적합한 분자량의 수지를 사용할 수도 있다.(A) Alkali-soluble resin contained in the positive photoresist composition of this invention is a novolak-type resin, polyvinyl alcohol, polyvinyl alkyl ether, the copolymer of styrene and acrylic acid, the copolymer of methacrylic acid and methacrylic acid alkyl ester It is preferable that it is 1 type, or 2 or more types chosen from the group which consists of a polymer of hydroxy styrene, polyvinylhydroxy benzoate, and polyvinyl hydroxybenzene. Here, it is preferable that (a) alkali-soluble resin uses novolak-type resin. The said novolak-type resin is a polymer synthesize | combined by making formaldehyde react with phenol, metacresol, paracresol which are aromatic alcohols, or a mixture thereof. In addition, in order to improve the performance of the photoresist, a polymer having a molecular weight suitable for the purpose may be used by removing a polymer, a medium molecule or a low molecule from the novolak-based resin.
본 발명의 포지티브 포토레지스트 조성물은 화학증폭형 포지티브 포토레지스트 조성물일 수도 있는데, 이 경우 (a) 알칼리 가용성 수지는 본래는 알칼리 수용액에 불용성 또는 난용성이지만, 산의 작용에 의해 알칼리 수용액에 가용성이 되는 수지인 것이 바람직하다. 여기서, 이러한 수지는 산의 작용에 의해 해리 가능한 보호기를 알칼리 수용액에 대해 가용성인 수지에 도입시킴으로써 수득한 수지를 말한다. 이러한 수지의 예로는, 히드록시기의 일부를 보호기로 보호한 히드록시스티렌 골격을 갖는 수지 및/또는 히드록시기를 보호기로 보호한 (메트)아크릴레이트 골격을 갖는 수지를 들 수 있다.The positive photoresist composition of the present invention may be a chemically amplified positive photoresist composition, in which case (a) the alkali soluble resin is originally insoluble or poorly soluble in aqueous alkali solution, but becomes soluble in aqueous alkali solution by the action of acid. It is preferable that it is resin. Here, such resin refers to a resin obtained by introducing a protecting group that can be dissociated by the action of an acid into a resin that is soluble to an aqueous alkali solution. Examples of such a resin include a resin having a hydroxystyrene skeleton in which a part of a hydroxy group is protected with a protecting group and / or a resin having a (meth) acrylate skeleton in which a hydroxyl group is protected with a protecting group.
상기 (a) 알칼리 가용성 수지는 조성물 총 중량에 대하여 3 내지 25 중량%로 포함되는 것이 바람직하다. 상술한 범위를 만족하면, 해상도 및 프로파일 형상이 우수해지는 이점이 있다.
The (a) alkali-soluble resin is preferably contained in 3 to 25% by weight based on the total weight of the composition. If the above range is satisfied, there is an advantage that the resolution and the profile shape are excellent.
본 발명의 포지티브 포토레지스트 조성물에 포함되는 (b) 감광성 화합물은 디아지드계 화합물을 이용하는 것이 바람직하다. 상기 디아지드계 화합물은 특별히 한정하지 않으나, 폴리히드록시 벤조페논과 1,2-나프토퀴논디아지드, 2-디아조-1-나프톨-5-설포닉산 및 2-디아조-1-나프톨-4-설포닉산로 이루어진 군에서 선택되는 1종 또는 2종 이상을 이용할 수 있다. It is preferable to use a diazide type compound for the (b) photosensitive compound contained in the positive photoresist composition of this invention. The diazide compound is not particularly limited, but polyhydroxy benzophenone, 1,2-naphthoquinone diazide, 2-diazo-1-naphthol-5-sulphonic acid and 2-diazo-1-naphthol- 1 type, or 2 or more types chosen from the group which consists of 4-sulphonic acid can be used.
본 발명의 포지티브 포토레지스트 조성물이 화학증폭형 포지티브 포토레지스트일 경우, (b) 감광성 화합물은 빛 또는 방사선의 작용에 의해 산을 발생하는 화합물은 광산발생제인 것이 바람직하다. 상기 광산발생제는, 물질 자체 또는 이러한 물질을 함유하는 레지스트 조성물에 자외선, 원자외선, 전자선, X-선, 또는 방사광과 같은 고에너지의 방사선을 조사함으로써 산을 생성시키는 물질이다. 상기 광산발생제로부터 생성되는 산은 수지에 작용하여 수지에 존재하는 산에 불안정한 기를 해리시킨다. When the positive photoresist composition of the present invention is a chemically amplified positive photoresist, (b) the photosensitive compound is preferably a compound which generates an acid by the action of light or radiation is a photoacid generator. The photoacid generator is a substance which generates an acid by irradiating the substance itself or a resist composition containing such substance with high energy radiation such as ultraviolet rays, far ultraviolet rays, electron beams, X-rays, or radiant light. The acid generated from the photoacid generator acts on the resin to dissociate the group that is unstable in the acid present in the resin.
상기 광산발생제는 오늄염 화합물, s-트리아진계 유기 할로겐 화합물, 설폰 화합물, 설포네이트 화합물 등을 포함한다. 특정하게는, 다음 화합물이 열거된다:The photoacid generator includes an onium salt compound, an s-triazine-based organic halogen compound, a sulfone compound, a sulfonate compound, and the like. Specifically, the following compounds are listed:
디페닐요도늄 트리플루오로메탄설포네이트, 4-메톡시페닐페닐요도늄 헥사플루오로안티모네이트, 4-메톡시페닐페닐요도늄 트리플루오로메탄설포네이트, 비스(4-t-부틸페닐)요도늄 테트라플루오로보레이트, 비스(4-t-부틸페닐)요도늄 헥사플루오로포스페이트, 비스(4-t-부틸페닐)요도늄 헥사플루오로안티모네이트, 비스(4-t-부틸페닐)요도늄 트리플루오로메탄설포네이트, 트리페닐설포늄 헥사플루오로포스페이트, 트리페닐설포늄 헥사플루오로안티모네이트, 트리페닐설포늄 트리플루오로메탄설포네이트, 4-메틸페닐디페닐설포늄 퍼플루오로부탄설포네이트, 4-메틸페닐디페닐설포늄 퍼플루오로옥탄설포네이트, 4-메톡시페닐디페닐설포늄 헥사플루오로안티모네이트, 4-메톡시페닐디페닐설포늄 트리플루오로메탄설포네이트, p-톨릴디페닐설포늄 트리플루오로메탄설포네이트, 2,4,6-트리메틸페닐디페닐설포늄 트리플루오로메탄설포네이트, 4-t-부틸페닐디페닐설포늄 트리플루오로메탄설포네이트, 4-페닐티오페닐디페닐설포늄 헥사플루오로포스페이트, 4-페닐티오페닐디페닐설포늄 헥사플루오로안티모네이트, 1-(2-나프톨릴메틸)티올라늄 헥사플루오로안티모네이트, 1-(2-나프톨릴메틸)티올라늄 트리플루오로메탄설포네이트, 4-히드록시-1-나프틸디메틸설포늄 헥사플루오로안티모네이트, 4-히드록시-1-나프틸디메틸설포늄트리플루오로메탄설포네이트, 2-메틸-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2,4,6-트리스(트리클로로메틸)-1,3,5-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(4-클로로페닐)-4,6-비스(트리클로로메틸)-1,3-5-트리아진, 2-(4-메톡시페닐)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(4-메톡시-1-나프틸)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(벤조[d][1,3]디옥솔란-5-일)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(4-메톡시스티릴)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(3,4,5-트리메톡시스티릴)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(3,4-디메톡시스티릴)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(2,4-디메톡시스티릴)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(2-메톡시스티릴)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(4-부톡시스티릴)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(4-펜틸옥시스티릴)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 1-벤조일-1-페닐메틸 p-톨루엔설포네이트(통상, '벤조인 토실레이트'라고 함), 2-벤조일-2-히드록시-2-페닐에틸 p-톨루엔설포네이트 (통상, 'α-메틸올벤조인 토실레이트'라고 함), 1,2,3-벤젠톨릴 트리메탄설포네이트,2,6-디니트로벤질 p-톨루엔설포네이트, 2-니트로벤질 p-톨루엔설포네이트,4-니트로벤질 p-톨루엔설포네이트, 디페닐 디설폰, 디-p-톨릴 디설폰, 디스(페닐설포닐)디아조메탄, 비스(4-클로로페닐설포닐)디아조메탄, 비스(p-톨릴설포닐)디아조메탄, 비스(4-3급-부틸페닐설포닐)디아조메탄, 비스(2,4-크실릴설포닐)디아조메탄, 비스(시클로헥실설포닐)디아조메탄, (벤조일)(페닐설포닐)디아조메탄, N-(페닐설포닐옥시)석신이미드, N-(트리플루오로메틸설포닐옥시)석신이미드, N-(트리플루오로메틸설포닐옥시)프탈이미드, N-(트리프루오로메틸설포닐옥시)-5-노르보르넨-2,3-디카복시이미드, N-(트리플루오로메틸설포닐옥시)나프탈이미드, N-(10-캄포르설포닐옥시)나프탈이미드, 4-메톡시-α-[[[(4-메틸페닐)설포닐]옥시]이미노]벤젠아세토니트릴 등이 포함된다.Diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium hexafluoroantimonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) Iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) Iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, 4-methylphenyldiphenylsulfonium perfluoro Butanesulfonate, 4-methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, p-tolyldiphenylsulfonium triple Oromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium Hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphtolylmethyl) thiolanium hexafluoroantimonate, 1- (2-naphtolylmethyl) thi Olanium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 2-methyl -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3-5-triazine, 2- (4 -Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (benzo [d] [1,3] dioxolane-5 -Yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxy Styryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxystyryl) -4 , 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 1-benzoyl-1-phenylmethyl p-toluenesulfonate (commonly referred to as' benzoin tosylate '), 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonate (usually' α- Methylolbenzoin tosylate '), 1,2,3-benzenetolyl Trimethanesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, 4-nitrobenzyl p-toluenesulfonate, diphenyl disulfone, di-p-tolyl disulfone , Dis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (4-tert-butylphenylsulfonyl) diazo Methane, bis (2,4-xylylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, (benzoyl) (phenylsulfonyl) diazomethane, N- (phenylsulfonyloxy) succinate Mead, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) -5-norbornene -2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (10-camphorsulfonyloxy) naphthalimide, 4-methoxy-α-[[ [(4-methylphenyl) sulfonyl] oxy] imino] benzeneacetonitrile, etc. Included.
상기 (b) 감광성 화합물은 조성물 총 중량에 대하여, 0.01 내지 5 중량%로 함유되는 것이 바람직하다. 상술한 범위를 만족하면, 감도, 해상도 및 프로파일 모양에 이점이 있다.
The photosensitive compound (b) is preferably contained in 0.01 to 5% by weight based on the total weight of the composition. If the above range is satisfied, there is an advantage in sensitivity, resolution, and profile shape.
본 발명의 포지티브 포토레지스트 조성물에 포함되는 (c) 용매는 하기 화학식 1로 표시되는 화합물과 유기용매를 포함한다. The solvent (c) included in the positive photoresist composition of the present invention includes a compound represented by the following Chemical Formula 1 and an organic solvent.
<화학식 1><Formula 1>
하기 화학식 1로 표시되는 화합물이 상기 (c) 용매 내에 포함되면, 주변의 온도 변화 및 장시간에 걸친 보존 안정성이 향상되는 이점이 있다.When the compound represented by the following formula (1) is included in the solvent (c), there is an advantage that the change in ambient temperature and storage stability over a long time are improved.
상기 유기용매는 상기 (a) 알칼리 가용성 수지 및 (b) 감광성 화합물을 용해시키고 적합한 건조 속도를 나타내며 용매 증발 후 균일하고 매끄러운 피막을 제공하는 것이라면, 특별히 한정하지 않는다. 상기 유기용매의 예로는 에틸셀로솔브 아세테이트, 메틸셀로솔브 아세테이트 및 프로필렌 글리콜 모노메틸 에테르 아세테이트와 같은 글리콜 에테르 에스테르; 프로필렌 글리콜 모노메틸 에테르와 같은 글리콜 에테르; 에틸 락테이트, 부틸 아세테이트, 아밀 아세테이트 및 에틸 피루베이트와 같은 에스테르; 아세톤, 메틸 이소부틸 케톤, 2-헵타논 및 시클로헥사논과 같은 케톤; γ-부티로락톤과 같은 시클릭 에스테르; 3-메톡시-1-부탄올 등과 같은 알코올 등을 들 수 있다. The organic solvent is not particularly limited as long as it dissolves the (a) alkali-soluble resin and (b) photosensitive compound, exhibits a suitable drying rate, and provides a uniform and smooth film after evaporation of the solvent. Examples of the organic solvent include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; Glycol ethers such as propylene glycol monomethyl ether; Esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; Ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; Alcohol, such as 3-methoxy- 1-butanol, etc. are mentioned.
상기 화학식 1로 표시되는 화합물과 유기용매는 상기 (c) 용매 내에 1:99 내지 10:90의 중량비로 포함되는 것이 바람직하다. 상술한 범위를 만족하면, 주변의 온도 변화 및 장시간에 걸친 보존 안정성의 향상되는 이점이 있다.The compound represented by Chemical Formula 1 and the organic solvent are preferably included in a weight ratio of 1:99 to 10:90 in the solvent (c). If the above range is satisfied, there is an advantage of improving the ambient temperature change and the storage stability over a long time.
상기 (c) 용매의 함량은 본 발명의 포지티브 포토레지스트 조성물이 용액 상태로 존재할 수 있고, 조성물 총 중량이 100중량%가 되도록 잔량이 포함되는 것이 바람직하다.The content of the solvent (c) may be present in the positive photoresist composition of the present invention in a solution state, and the remaining amount is preferably included so that the total weight of the composition is 100% by weight.
또한, 본 발명의 포지티브 포토레지스트 조성물에는 필요에 따라 착색제, 염료, 가소제, 속도증진제, 계면활성제 등의 첨가제를 첨가할 수 있다. 이러한 첨가제를 함유한 포토레지스트 조성물을 기판에 피복함으로써 개별공정의 특성에 따른 성능향상을 도모할 수도 있다.
Moreover, additives, such as a coloring agent, dye, a plasticizer, a speed increasing agent, surfactant, can be added to the positive photoresist composition of this invention as needed. By coating the photoresist composition containing such an additive on the substrate, it is possible to improve the performance according to the characteristics of the individual process.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예 1 내지 실시예 5, 비교예 1 및 비교예 2: 포지티브 포토레지스트의 제조Examples 1 to 5, Comparative Example 1 and Comparative Example 2: Preparation of Positive Photoresist
표 1에 제시된 수지, 감광성 화합물 및 퀀쳐를 제시된 중량부(고형분으로 환산된 것)로 용매에 용해시키고, 교반시킨 후, 기공 직경이 0.1㎛인 필터로 여과시켜 포토레지스트 조성물을 제조하였다.The resin, photosensitive compound and quencher shown in Table 1 were dissolved in a solvent in the indicated parts by weight (in terms of solids), stirred, and filtered with a filter having a pore diameter of 0.1 μm to prepare a photoresist composition.
A-1: 히드록시스티렌의 하이드록시기에 대해 에톡시에틸기/아이소프로필기 보호기를 함유한 분자량 20,000, 분산도 1.7의 수지로 에톡시에틸기의 보호율 30%, 아이소프로필기의 보호율 10%A-1: 30% of ethoxyethyl group, 10% of isopropyl group with a molecular weight of 20,000 containing a ethoxyethyl group / isopropyl group protecting group and a dispersity of 1.7 with respect to the hydroxy group of hydroxystyrene
B-1: 비스(부틸설포닐)디아조메탄B-1: bis (butylsulfonyl) diazomethane
C-1: 프로필렌 글리콜 모노메틸 에테르 아세테이트C-1: Propylene Glycol Monomethyl Ether Acetate
C-2: 프로필렌 글리콜 모노메틸 에테르C-2: Propylene Glycol Monomethyl Ether
C-3: 테트라히드로 푸르푸릴알콜C-3: tetrahydrofurfuryl alcohol
D-1: 트리스(2-(2-메톡시에톡시)에틸)아민
D-1: tris (2- (2-methoxyethoxy) ethyl) amine
시험예: 포토레지스트 조성물의 성능 테스트Test Example: Performance Test of Photoresist Composition
상기에서 제조한 레지스트 용액을 각각 23℃, 40℃에 보관한 후 입도분석을 30일 간격으로 180일간 측정하여 표 2에 나타내었다. 여기서, 입자수는 0.3㎛ 이상의 것의 개수이다The resist solution prepared above was stored at 23 ° C. and 40 ° C., respectively, and then measured for 180 days at 30 day intervals. Here, the number of particles is the number of 0.3 µm or more.
또한 30일 간격으로 상기 제조한 레지스트 용액을 헥사메틸디실라잔으로 처리된 실리콘 웨이퍼에 스핀 피복기를 사용하여 도포하였고, 건조시킨 후의 막두께가 1.208㎛이었다. 레지스트 용액을 도포한 후, 100℃의 열판에서 60초 동안 예비 열처리를 수행하였다. 이와 같이 형성된 레지스트 필름을 갖는 웨이퍼를 노광 파장이 248㎚(KrF)인 스캔 방식 노광기['NSR-S203B', 제조원: Nikon Corp., NA = 0.68, σ=0.75]를 사용하여 노광량을 서서히 변화시키면서 노광시켜 라인 및 스페이스 패턴을 형성시켰다. 이어서, 열판에서, 노광 후 열처리를 110℃에서 60초 동안 수행하였다. 추가로, 2.38% 테트라메틸암모늄히드록사이드 수용액을 사용하여 60초 동안 패들 현상을 수행하였다. 현상 후의 패턴을 KLA 주사 전자 현미경을 사용하여 0.3㎛ 라인 및 스페이스 패턴에서 프로파일을 측정하였고, 결과는 표 2에 나타내었다.Further, the prepared resist solution was applied to a silicon wafer treated with hexamethyldisilazane at 30-day intervals using a spin coater, and the film thickness after drying was 1.208 µm. After applying the resist solution, preheat treatment was performed for 60 seconds on a hot plate at 100 ° C. The wafer having the resist film thus formed was gradually exposed to light using a scanning exposure apparatus ['NSR-S203B' manufactured by Nikon Corp., NA = 0.68, sigma == 0.75], having an exposure wavelength of 248 nm (KrF). Exposure was performed to form line and space patterns. Subsequently, in the hot plate, post-exposure heat treatment was performed at 110 ° C. for 60 seconds. In addition, paddle development was performed for 60 seconds using an aqueous 2.38% tetramethylammonium hydroxide solution. The pattern after development was measured using the KLA scanning electron microscope in the 0.3 micrometer line and space pattern, and the result is shown in Table 2.
레지스트 패턴 프로파일이 좋은 경우 ○, 레지스트 패턴 프로파일이 나쁜경우에는 X로 표기하였다. (Circle) when a resist pattern profile is good, and X when a resist pattern profile is bad.
* 입도 단위: 개/ml
* Granularity Unit: pcs / ml
표 2에 나타난 바와 같이, 본 발명에 따른 테트라히드로 푸르푸릴알콜의 유기용매를 함유할 경우 온도 변화 및 장시간 보관에 따른 재석출에 의한 파티클 발생이 없어 입도 안정성을 지님을 알 수 있다.
As shown in Table 2, when containing the organic solvent of tetrahydrofurfuryl alcohol according to the present invention it can be seen that there is no particle generation by reprecipitation due to temperature changes and long-term storage it has a particle size stability.
Claims (5)
(b) 감광성 화합물; 및
(c) 하기 화학식 1로 표시되는 화합물과 유기용매를 포함하는 용매를 포함하는 것을 특징으로 하는 포지티브 포토레지스트 조성물:
<화학식 1>
(b) photosensitive compounds; And
(c) a positive photoresist composition comprising a solvent comprising a compound represented by Formula 1 below and an organic solvent:
<Formula 1>
상기 (a) 알칼리 가용성 수지 3 내지 25중량%,
상기 (b) 감광성 화합물 0.03 내지 1.75중량%; 및
상기 (c) 화학식 1로 표시되는 화합물과 유기용매를 포함하는 용매 잔량을 포함하는 것을 특징으로 하는 포지티브 포토레지스트 조성물. The method according to claim 1,
3 to 25% by weight of the above (a) alkali-soluble resin,
0.03 to 1.75 wt% of the photosensitive compound (b); And
(C) A positive photoresist composition comprising a residual amount of a solvent comprising a compound represented by Formula 1 and an organic solvent.
상기 (a) 알칼리 가용성 수지는 노볼락계 수지, 폴리비닐알코올, 폴리비닐알킬에테르, 스티렌과 아크릴산의 공중합체, 메타크릴산과 메타크릴산 알킬에스테르와의 공중합체, 히드록시스티렌의 중합체, 폴리비닐히드록시벤조에이트 및 폴리비닐히드록시벤젠으로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것을 특징으로 하는 포지티브 포토레지스트 조성물.The method according to claim 1,
The alkali-soluble resin (a) is a novolak-based resin, polyvinyl alcohol, polyvinyl alkyl ether, copolymer of styrene and acrylic acid, copolymer of methacrylic acid and methacrylic acid alkyl ester, polymer of hydroxy styrene, polyvinyl Positive photoresist composition, characterized in that one or two or more selected from the group consisting of hydroxybenzoate and polyvinylhydroxybenzene.
상기 (b) 감광성 화합물은 디아지드계 화합물인 것을 특징으로 하는 포지티브 포토레지스트 조성물.The method according to claim 1,
(B) The photosensitive compound is a positive photoresist composition, characterized in that the diazide compound.
상기 화학식 1로 표시되는 화합물과 유기용매는 1:99 내지 10:90의 중량비로 포함되는 것을 특징으로 하는 포지티브 포토레지스트 조성물.The method according to claim 1,
Positive photoresist composition, characterized in that the compound represented by the formula (1) and the organic solvent is included in a weight ratio of 1:99 to 10:90.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20130099848A (en) * | 2012-02-29 | 2013-09-06 | 도오꾜오까고오교 가부시끼가이샤 | Resist composition and method of forming resist pattern |
| US11822242B2 (en) | 2019-11-14 | 2023-11-21 | Merck Patent Gmbh | DNQ-type photoresist composition including alkali-soluble acrylic resins |
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| JP2000275828A (en) | 1999-03-25 | 2000-10-06 | Fuji Photo Film Co Ltd | Photosensitive composition and original plate of planographic printing plate using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20130099848A (en) * | 2012-02-29 | 2013-09-06 | 도오꾜오까고오교 가부시끼가이샤 | Resist composition and method of forming resist pattern |
| JP2013182083A (en) * | 2012-02-29 | 2013-09-12 | Tokyo Ohka Kogyo Co Ltd | Resist composition and method of forming resist pattern |
| US11822242B2 (en) | 2019-11-14 | 2023-11-21 | Merck Patent Gmbh | DNQ-type photoresist composition including alkali-soluble acrylic resins |
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