KR100635506B1 - Method for forming resist pattern - Google Patents

Method for forming resist pattern Download PDF

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KR100635506B1
KR100635506B1 KR1020050112405A KR20050112405A KR100635506B1 KR 100635506 B1 KR100635506 B1 KR 100635506B1 KR 1020050112405 A KR1020050112405 A KR 1020050112405A KR 20050112405 A KR20050112405 A KR 20050112405A KR 100635506 B1 KR100635506 B1 KR 100635506B1
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resist
resist film
heat generating
film
layer
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KR1020050112405A
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Korean (ko)
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권영길
이성택
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삼성에스디아이 주식회사
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/265—Selective reaction with inorganic or organometallic reagents after image-wise exposure, e.g. silylation
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Architecture (AREA)
  • Chemical & Material Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Materials For Photolithography (AREA)

Abstract

A method for forming a resist pattern is provided to reduce fabrication costs by irradiating a laser beam onto a selected region alone using a heat generating layer. A resist layer(11b) is formed on a substrate(10). A pre-bake is performed on the resist layer. An exposure process is performed on the resultant structure. A heat generating layer(12) is formed on the resist layer. A post exposure bake is performed on a selected region of the resist layer by irradiating a laser beam onto a predetermined portion of the heat generating layer. A silylation process is performed on the resist layer using a silylation agent. A developing process is performed thereon.

Description

레지스트의 패턴형성방법{Method for forming resist pattern}Pattern forming method of resist {Method for forming resist pattern}

도 1a 내지 1g는 본 발명의 일실시예의 의한 레지스트의 패턴형성방법을 설명하기 위한 단면도.1A to 1G are cross-sectional views illustrating a method for forming a resist pattern according to an embodiment of the present invention.

- 도면부호에 대한 간단한 설명--Brief description of the drawings

10 : 기판 11 : 레지스트10 substrate 11 resist

12 : 열발생층 12a: 기재층12: heat generating layer 12a: base material layer

12b: 광열변환층 12b: photothermal conversion layer

본 발명은 레지스트의 패턴형성방법에 관한 것으로, 더욱 상세하게는 TIPS 공정(Top Surface Imaging Process)에서 레지스트막 상에 위치한 열발생층의 일부분에 레이저를 조사하여 선택영역의 표면을 후굽기(post exposure bake) 공정을 진행하는 레지스트의 패턴형성방법에 관한 것이다.The present invention relates to a pattern forming method of a resist, and more particularly, to post-expose a surface of a selected region by irradiating a laser to a portion of a heat generating layer on a resist film in a TIPS process (Top Surface Imaging Process). bake) The present invention relates to a pattern formation method of a resist undergoing a process.

일반적은 포토리소그래피 공정의 문제점으로는 빛이 도달한 기판의 영향을 많이 받는점, 노칭(notching), 정재파 효과(standing wave effect), 패턴 붕괴(pattern collapse), 선폭 균일성(CD uniformity) 불량, 선폭 직선도(CD linearity)불량, IG 바이어스(Isolated & Grouped Bias)등이 있다. 상기 문제점의 해결책으로 TIPS 공정(Top Surface Imaging Process)이 연구되고 있다. TIPS 공정의 특징은 근접 노광(Shallow exposure)을 하며, 노광, 비노광 지역에 선택적으로 확산 반응이 일어서 잠재적 상(latent image)을 형성한다는 것이다. 실리레이션(silylation)된 지역은 마스크 역할을 하고 실리레이션 되지 않은 지역은 O2 플라즈마 등에 의해 건식 현상(dry develop)된다. 따라서 에너지 흡수계수가 큰 레지스트가 요구되며, O2 플라즈마 식각시 큰 선택비를 갖는 공정조건이 필요하다.Common photolithography problems include the effects of light reaching the substrate, notching, standing wave effects, pattern collapse, poor CD uniformity, CD linearity defects and IG bias (Isolated & Grouped Bias). As a solution to the above problem, the TIPS process (Top Surface Imaging Process) has been studied. A feature of the TIPS process is that it has a shallow exposure, and a selective diffusion reaction occurs in the exposed, non-exposed areas to form a latent image. The silized area serves as a mask and the unsilified area is dry developed by O 2 plasma or the like. Therefore, a resist having a large energy absorption coefficient is required, and a process condition having a large selectivity when etching an O 2 plasma is required.

이러한 TIPS 공정은 단층 레지스트 공정이며, 이 공정을 사용하면 정재파효과, 다중간섭효과, 노칭 현상을 제가할 수 있고, 해상도 및 초점심도(depth of focus: DOF)를 증가시킬 수 있다는 장점이 있다.This TIPS process is a single layer resist process, which can eliminate standing wave effects, multiple interference effects, notching, and increase resolution and depth of focus (DOF).

종래의 TIPS 공정은 기판 상에 에너지 흡수계수가 큰 레지스트를 형성하고 상기 레지스트를 선굽기(pre-baking)를 한다. 그 후 상기 선굽기된 레지스트를 마스크를 이용하여 선택 노광하고, 상기 노광된 포토레지스트를 후굽기(post exposure bake)를 한다. 상기 후굽기된 레지스트막의 표면에 실릴레이션 공정을 수행하고, 상기 실릴레이션 된 부분을 마스크로 하여 레지스트막을 건식현상하는 단계를 포함한다. The conventional TIPS process forms a resist having a high energy absorption coefficient on a substrate and pre-baks the resist. Thereafter, the precured resist is selectively exposed using a mask, and the exposed photoresist is subjected to post exposure bake. And performing a silylation process on the surface of the bent resist film, and dry developing the resist film using the silylated portion as a mask.

그러나 종래의 TIPS 공정은 마스크가 꼭 필요하며 마스크를 사용하지 않고 패턴형성이 불가능하다는 단점이 있고, 이러한 마스크는 가격이 비싸 제조원가를 상승시키는 문제점이 있다.However, the conventional TIPS process has a disadvantage in that a mask is necessary and pattern formation is impossible without using a mask, and such a mask has a problem of increasing manufacturing cost due to high price.

따라서 본 발명은 상기와 같은 종래 기술의 제반 단점과 문제점을 해결하기 위한 것으로, 본 발명은 마스크 없이 공정을 진행하여 제조원가를 절감시킬 수 있는 레지스트의 패턴형성방법을 제공한다.Therefore, the present invention is to solve all the disadvantages and problems of the prior art as described above, the present invention provides a pattern forming method of a resist that can reduce the manufacturing cost by proceeding without a mask.

본 발명은 상기 기술적 과제를 해결하기 위하여, 기판을 제공하는 단계; 상기 기판 상에 레지스트막을 형성하는 단계; 상기 레지스트막을 선굽기(prebake)하는 단계; 상기 레지스트막을 노광하는 단계; 상기 노광된 레지스트막 상에 열발생층을 라미네이션(lamination)하는 단계; 상기 열발생층의 일부분에 레이저를 조사하여 상기 노광된 레지스트막의 선택영역을 후굽기(post exposure bake)하는 단계; 상기 후굽기된 레지스트막을 실릴화제(silyation agent)를 이용하여 실리레이션(silyation)시키는 단계; 상기 실리레이션된 레지시트막을 현상하는 단계; 를 포함하는 것을 특징으로 하는 레지스트의 패턴형성방법을 제공한다.The present invention, to solve the above technical problem, providing a substrate; Forming a resist film on the substrate; Prebake the resist film; Exposing the resist film; Laminating a heat generating layer on the exposed resist film; Irradiating a portion of the heat generating layer with a laser to bake a selected area of the exposed resist film; Silicifying the bent resist film using a silylation agent; Developing the silized resist sheet film; It provides a pattern forming method of a resist comprising a.

본 발명의 상기 목적과 기술적 구성 및 그에 따른 작용효과에 관한 자세한 사항은 본 발명의 바람직한 실시 예를 도시하고 있는 도면을 참조한 이하 상세한 설명에 의해 보다 명확하게 이해될 것이다. 또한 도면들에 있어서, 층 및 영역의 길이, 두께 등은 편의를 위하여 과장되어 표현될 수도 있다. 명세서 전체에 걸쳐서 동일한 참조번호들은 동일한 구성요소들을 나타낸다.Details of the above objects and technical configurations and the effects thereof according to the present invention will be more clearly understood by the following detailed description with reference to the drawings showing preferred embodiments of the present invention. In addition, in the drawings, the length, thickness, etc. of layers and regions may be exaggerated for convenience. Like numbers refer to like elements throughout.

도 1a 내지 도 1g는 본 발명의 일실시예에 의한 레지스트의 패턴형성방법을 설명하기 위한 단면도이다.1A to 1G are cross-sectional views illustrating a method for forming a pattern of a resist according to an embodiment of the present invention.

도 1a 내지 도 1g를 참조하면, 기판(10) 상에 레지스트막(11)을 형성한다. 1A to 1G, a resist film 11 is formed on the substrate 10.

상기 레지스트막(11)은 에너지 흡수계수가 큰 것을 특징으로 하며, 산에 민감한 보호기를 포함한다. 또한, 광산발생제와 유기염기를 더욱 포함할 수 있다. The resist film 11 is characterized by a large energy absorption coefficient, and includes an acid-sensitive protecting group. In addition, it may further include a photoacid generator and an organic base.

상기 산에 민감한 보호기가 붙어있는 레지스트는 알칼리 현상액에 의해 용해되는 것이 억제되고, 후공정의 노광에 의해 발생된 산에 의해 산에 민감한 보호기가 탈리되면 레지스트가 현상액에 용해될 수 있게 된다. 상기 산에 민감한 보호기는 t-부틸, 테트라히드로피란일, 메틸테트라히드로피란일, 테트라히드로퓨란일, 메틸테프라히드로퓨란일, 메톡시에틸, 2-메톡시프로필, 에폭시에틸, 2-에톡시프로필, t-부톡시에틸, 아세톡시에톡시에틸, 아세톡시메틸, t-부톡시카르보닐 및 이소부톡시에틸 등을 사용할 수 있다. The resist with the protecting group sensitive to the acid is suppressed from being dissolved by the alkaline developer, and the resist can be dissolved in the developing solution when the protecting group sensitive to the acid is released by the acid generated by the exposure in the subsequent step. The acid sensitive protecting groups are t-butyl, tetrahydropyranyl, methyltetrahydropyranyl, tetrahydrofuranyl, methylteprahydrofuranyl, methoxyethyl, 2-methoxypropyl, epoxyethyl, 2-ethoxypropyl , t-butoxyethyl, acetoxyethoxyethyl, acetoxymethyl, t-butoxycarbonyl, isobutoxyethyl and the like can be used.

상기 광산발생제로는 빛에 의해 산을 발생할 수 있는 화합물이면 무엇이든 사용가능하며, 주로 157nm와 193nm에서 상대적으로 흡광도가 적은 프탈이미도트리플루오르메탄술포테이트(phthalimido trifluoromethane sulfonate), 디니트로벤질토실레이트(dinitrobenzyltosylate), n-데실디술폰(n-decyl disulfone) 및 나프틸이미도트리플루오로메탄술포네이트(naphthylimido triflouromethane sulfonate)로 이루어진 군으로부터 선택되는 것을 사용하는 것이 바람직하고, 이와 함께 디페닐요도염 헥사플루오르포스페이트, 디페닐요도염 헥사플루오르 아르세네이트, 디페닐요도염 헥사플루오르안티모네이트, 디페닐파라메톡시페닐설포늄 트리플레이트, 디페닐파라톨루에닐설포늄 트리플레이트, 디페닐파라이소부틸페닐설포늄 트리플레이트, 트리페닐설포늄 헥사플루오르 아르세네이트, 트리페닐설포늄 헥사플루오르 안 티모네이트, 트리페닐설포늄 트리플레이트 및 디부틸나프틸설포늄 트리플레이트로 이루어진 군으로부터 선택된 황화염계 또는 오니움염계 화합물을 겸용할 수 있다. As the photoacid generator, any compound capable of generating an acid by light may be used, and phthalimido trifluoromethane sulfonate having relatively low absorbance at 157 nm and 193 nm and dinitrobenzyltosylate ( dinitrobenzyltosylate), n-decyl disulfone, and naphthylimido triflouromethane sulfonate are preferably used, together with diphenylurodoxyl hexafluorophosphate. , Diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxy phenylsulfonium triflate, diphenyl paratoluenylsulfonium triflate, diphenyl paraisobutyl phenyl sulfonium triflate , Triphenylsulfonium hexafluoro arsenate, tri Nilseol phosphonium hexafluorotitanate not Timothy sulfonate, triphenyl sulfonium triflate and dibutyl naphthyl tilseol phosphonium tree sulfate- based or selected from the group consisting of a plate of sludge can also be used to help salt-based compound.

상기 유기용매는 통상적으로 사용되는 유기용매는 무엇이든 사용가능하며, 바람직하게는 에틸 3-에톡시프로피오네이트, 메틸 3-메톡시 프로피오네이트, 사이크로헥사논, 프로필렌글리콜 메틸에테를아세테이트, n-헵타논 및 에틸 락테이트로 이루어진 군으로부터 선택된 것을 사용할 수 있다.The organic solvent may be any organic solvent that is commonly used, preferably ethyl 3-ethoxypropionate, methyl 3-methoxy propionate, cyclohexanone, propylene glycol methyl ether acetate , n-heptanone and ethyl lactate can be used.

상기 유기용매는 상기 레지스트막을 원하는 두께로 도포하기 위하여 사용된다.The organic solvent is used to apply the resist film to a desired thickness.

이어서, 상기 레지스트막(11)을 선굽기(pre-baking)를 한다. 선굽기 방법으로는, 핫플레이트와 기판 사이에 간극을 두는 프록시미티 베이크를 행하는 것이 바람직하다. 상기 선굽기는 레지스트 조성물내에 존재하는 용매를 열에너지에 의해 증발시켜 고형의 레지스트 필름상태를 유지하는 공정이다.Subsequently, the resist film 11 is pre-baked. As the roasting method, it is preferable to perform a proximity baking with a gap between the hot plate and the substrate. The roasting is a process of maintaining a solid resist film state by evaporating a solvent present in the resist composition by thermal energy.

이어서, 상기 선굽기된 레지스트막(11a)을 노광시킨다. 상기 노광공정은 투과하는 빛이 레지스트의 광화학 반응을 일어나게 하여 이미 형성된 패턴과의 중첩정확도(overlay accuracy)를 유지하는 공정이다. 상기 노광공정에 의해 생성된 산(H+)에 의해서 레지스트 중합체에서 보호기가 탈리되는 화학반응이 일어나 용해도의 차이가 유발된다.Subsequently, the precured resist film 11a is exposed. The exposure step is a step in which the transmitted light causes the photochemical reaction of the resist to maintain the overlay accuracy with the already formed pattern. The acid (H + ) generated by the exposure process causes a chemical reaction in which the protecting group is released from the resist polymer, thereby causing a difference in solubility.

상기 노광된 레지스트막(11b) 상에 기재층(12a) 및 광열변환층(12b)으로 구성된 열발생층(12)을 라미네이션(lamination)한다.The heat generating layer 12 including the base layer 12a and the photothermal conversion layer 12b is laminated on the exposed resist film 11b.

상기 기재층(12a)은 상기 광-열 변환층(12b)에 빛을 전달하기 위하여 투명성을 가져야 하며, 적당한 광학적 성질과 충분한 기계적 안정성을 가진 물질로 이루어질 수 있다. 예를 들면, 폴리에스테르, 폴리아크릴, 폴리에폭시, 폴리에틸렌 및 폴리스틸렌으로 이루어진 군에서 선택되는 하나 이상의 고분자 물질이거나 유리로 이루어질 수 있다. 더욱 바람직하게는 상기 기재층(12a)은 폴리에틸렌테레프탈레이트일 수 있다. 상기 기재층(12a)의 역할은 지지기판으로서의 역할을 수행하며 복합적인 다중계도 사용 가능하다.The substrate layer 12a should have transparency to transmit light to the light-to-heat conversion layer 12b, and may be made of a material having suitable optical properties and sufficient mechanical stability. For example, it may be made of glass or at least one polymeric material selected from the group consisting of polyester, polyacrylic, polyepoxy, polyethylene and polystyrene. More preferably, the base layer 12a may be polyethylene terephthalate. The substrate layer 12a serves as a support substrate, and complex multiple systems may be used.

상기 광-열변환층(12b)은 적외선-가시광선 영역의 빛을 흡수하여 상기 빛의 일부분을 열로 변환시키는 층으로서, 적당한 광학밀도(optical density)를 가져야 하며, 빛을 흡수하기 위한 광흡수성 물질을 포함하는 것이 바람직하다. 여기서, 상기 광-열변환층(12b)은 Al, Ag 및 이들의 산화물 및 황화물로 이루어진 금속막이거나 카본 블랙, 흑연 또는 적외선 염료를 포함하는 고분자로 이루어진 유기막으로 이루어질 수 있다. 여기서, 상기 금속막은 진공 증착법, 전자빔 증착법 또는 스퍼터링을 이용하여 형성할 수 있으며, 상기 유기막은 통상적인 필름 코팅 방법으로서, 그라비아(Gravure), 압출(extrusion), 스핀(spin) 및 나이프(knife) 코팅방법 중에 하나의 방법에 의해 형성될 수 있다. The light-to-heat conversion layer 12b is a layer for absorbing light in the infrared-visible ray region and converting a portion of the light into heat, and having a suitable optical density, and a light absorbing material for absorbing light. It is preferable to include. Here, the light-to-heat conversion layer 12b may be a metal film made of Al, Ag, oxides and sulfides thereof, or an organic film made of a polymer including carbon black, graphite, or infrared dye. Here, the metal film may be formed by vacuum deposition, electron beam deposition, or sputtering, and the organic film is a conventional film coating method, and includes gravure, extrusion, spin, and knife coating. It can be formed by one of the methods.

이어서, 상기 열변생층(12)의 일부분에 레이저를 조사하여 상기 노광 된 레지스트막(11b)의 선택영역의 표면을 후굽기(post exposure bake)를 진행한다. Subsequently, a portion of the thermally modified layer 12 is irradiated with a laser to post-bake the surface of the selected region of the exposed resist film 11b.

이어서 상기 후굽기된 레지스트막(11c)을 실릴화제를 이용하여 실릴레이션하는 공정을 실행한다. 상기 실릴레이션 공정에 사용되는 실릴화제는 헥사메틸 디실 라잔, 테트라메틸 디실라잔, 비스디메틸아미노디메틸실란, 비스디메틸아미노 메틸실란, 디메틸실릴 디메틸아민, 디메틸실릴 디에틸아민, 트리메틸실릴 디메틸아민, 트리데틸실릴 디에틸아민 및 디메틸아미노 펜타메틸디실란으로 이루어진 군으로부터 선택되는 것이 바람직하다. 상기 실릴화제는 기체 또는 액체상태로 사용할 수 있다. 실릴레이션 반응구조는 중합체의 -OH기와 Si기가 Si-O 댕글링(dangling)결합을 이루게 된다. 댕글링 결합은 불안정한 결합이므로 외부로부터의 열에너지 또는 수분(H2O)인가시 Si가 쉽게 외부-확산(out-diffusion), 즉 디실레이션(desilation)된다. Subsequently, a process of silylating the baked resist film 11c using a silylating agent is performed. The silylating agent used in the silylation process is hexamethyl disilazane, tetramethyl disilazane, bisdimethylaminodimethylsilane, bisdimethylamino methylsilane, dimethylsilyl dimethylamine, dimethylsilyl diethylamine, trimethylsilyl dimethylamine, tri It is preferably selected from the group consisting of decylsilyl diethylamine and dimethylamino pentamethyldisilane. The silylating agent may be used in gas or liquid state. In the silylation reaction structure, the -OH group and the Si group of the polymer form a Si-O dangling bond. Dangling bond is unstable because it is combined with Si upon application of thermal energy or water (H 2 O) from the outside easily out-diffuse (out-diffusion), i.e. disil illustration (desilation).

이와 같이 상기 후굽기된 레지스트막상에 히드록시기가 생성된 부위에서만 실릴레이션이 집중적으로 일어나게 되며, 이를 마스크로 이용하여 불소계 또는 염소계 가스와 산소계 가스를 혼합하여 건식 식각을 진행하여, 레지스트패턴(11e)를 형성한다. 상기 레지스트패턴(11e)를 식각마스크로 사용하여 이후의 패턴형성공정을 진행한다.As described above, the silylation occurs intensively only at the site where the hydroxyl group is formed on the bent resist film, and dry etching is performed by mixing the fluorine-based or chlorine-based gas with the oxygen-based gas by using the mask as a mask to form the resist pattern 11e. Form. The resist pattern 11e is used as an etching mask, and then a pattern forming process is performed.

이와 같은 레지스트의 패턴형성방법은 마스크 없이 제조공정을 진행할 수 있어 제조원가를 절감할 수 있는 효과가 있다.Such a pattern formation method of the resist can proceed the manufacturing process without a mask has the effect of reducing the manufacturing cost.

본 발명은 이상에서 살펴본 바와 같이 바람직한 실시 예를 들어 도시하고 설명하였으나, 상기한 실시 예에 한정되지 아니하며 본 발명의 정신을 벗어나지 않는 범위 내에서 당해 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 다양한 변경과 수정이 가능할 것이다.Although the present invention has been shown and described with reference to the preferred embodiments as described above, it is not limited to the above embodiments and those skilled in the art without departing from the spirit of the present invention. Various changes and modifications will be possible.

본 발명은 열발생층을 이용하여 선택영역에만 레이저를 조사하여 레지스트의 패턴을 형성하는 것으로, 마스크 없이 레지스트의 패턴형성공정을 진행할 수 있어 제조원가를 절감할 수 있는 효과가 있다.The present invention is to form a pattern of the resist by irradiating a laser only to the selected region using the heat generating layer, it is possible to proceed with the pattern forming process of the resist without a mask, thereby reducing the manufacturing cost.

Claims (6)

기판을 제공하는 단계;Providing a substrate; 상기 기판 상에 레지스트막을 형성하는 단계;Forming a resist film on the substrate; 상기 레지스트막을 선굽기(prebake)하는 단계;Prebake the resist film; 상기 레지스트막을 노광하는 단계;Exposing the resist film; 상기 노광된 레지스트막 상에 열발생층을 라미네이션(lamination)하는 단계;Laminating a heat generating layer on the exposed resist film; 상기 열발생층의 일부분에 레이저를 조사하여 상기 노광된 레지스트막의 선택영역을 후굽기(post exposure bake)하는 단계;Irradiating a portion of the heat generating layer with a laser to bake a selected area of the exposed resist film; 상기 후굽기된 레지스트막을 실릴화제(silyation agent)를 이용하여 실리레이션(silyation)시키는 단계; 및Silicifying the bent resist film using a silylation agent; And 상기 실리레이션된 레지시트막을 현상하는 단계; 를 포함하는 것을 특징으로 하는 레지스트의 패턴형성방법.Developing the silized resist sheet film; Pattern forming method of a resist comprising a. 제 1 항에 있어서,The method of claim 1, 상기 레지스트는 t-부틸, 테트라히드로피란일, 메틸테트라히드로피란일, 테트라히드로퓨란일, 메틸테프라히드로퓨란일, 메톡시에틸, 2-메톡시프로필, 에폭시에틸, 2-에톡시프로필, t-부톡시에틸, 아세톡시에톡시에틸, 아세톡시메틸, t-부톡시카르보닐 및 이소부톡시에틸로 이루어진 군에서 선택되는 산에 민감한 보호기를 포함하는 레지스트인 것을 특징으로 하는 레지스트의 패턴형성방법.The resist is t-butyl, tetrahydropyranyl, methyltetrahydropyranyl, tetrahydrofuranyl, methylteprahydrofuranyl, methoxyethyl, 2-methoxypropyl, epoxyethyl, 2-ethoxypropyl, t- A pattern forming method of a resist, characterized in that it is a resist containing a protecting group sensitive to an acid selected from the group consisting of butoxyethyl, acetoxyethoxyethyl, acetoxymethyl, t-butoxycarbonyl and isobutoxyethyl. 제 1 항에 있어서,The method of claim 1, 상기 레지스트의 현상방법은 불소계 또는 염소계 가스와 산소계 가스를 혼합하여 건식 현상하는 것을 특징으로 하는 레지스트의 패턴형성방법.The resist development method is a pattern formation method of a resist, characterized in that the dry development by mixing fluorine-based or chlorine-based gas and oxygen-based gas. 제 1 항에 있어서,The method of claim 1, 상기 열발생층은 기재층, 광열변환층을 포함하는 것을 특징으로 하는 레지스트의 패턴형성방법.The heat generating layer is a pattern forming method of the resist, characterized in that it comprises a substrate layer, a photothermal conversion layer. 제 1 항에 있어서,The method of claim 1, 상기 실릴화제는 헥사메틸 디실라잔, 테트라메틸 디실라잔, 비스디메틸아미노 디메틸실란, 비스디메틸아미노 메틸실란, 디메틸실릴 디메틸아민, 트리메틸실릴 및 디메틸아미노 펜타메틸디실란으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 레지스트의 패턴형성방법.The silylating agent is selected from the group consisting of hexamethyl disilazane, tetramethyl disilazane, bisdimethylamino dimethylsilane, bisdimethylamino methylsilane, dimethylsilyl dimethylamine, trimethylsilyl and dimethylamino pentamethyldisilane. The pattern formation method of the resist made into. 제 2 항에 있어서,The method of claim 2, 상기 레지스트는 광산 발생제와 유기용매를 더욱 포함하는 것을 특징으로 하는 레지스트의 패턴형성방법.The resist pattern forming method of the resist, characterized in that further comprises a photoacid generator and an organic solvent.
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US9798241B2 (en) 2015-01-09 2017-10-24 Samsung Electronics Co., Ltd. Methods of manufacturing photomasks, methods of forming photoresist patterns and methods of manufacturing semiconductor devices

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US5491047A (en) 1993-06-03 1996-02-13 Kim; Hyeong Soo Method of removing a silylated or germanium implanted photoresist
JP2000112149A (en) 1998-10-02 2000-04-21 Nec Corp Forming method of resist pattern

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5491047A (en) 1993-06-03 1996-02-13 Kim; Hyeong Soo Method of removing a silylated or germanium implanted photoresist
JP2000112149A (en) 1998-10-02 2000-04-21 Nec Corp Forming method of resist pattern

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9798241B2 (en) 2015-01-09 2017-10-24 Samsung Electronics Co., Ltd. Methods of manufacturing photomasks, methods of forming photoresist patterns and methods of manufacturing semiconductor devices

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