KR20030021907A - Photosensitive polymer including pyranyl ether having fluorine substituted alkyl ester and resist composition comprising the same - Google Patents
Photosensitive polymer including pyranyl ether having fluorine substituted alkyl ester and resist composition comprising the same Download PDFInfo
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- 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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- 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
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
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- 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
- C08F232/08—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 condensed rings
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- 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
- C08F34/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
- C08F34/02—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring in a ring containing oxygen
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- 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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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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
- G03F7/0395—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
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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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- 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
Abstract
Description
본 발명은 감광성 폴리머 및 화학증폭형 레지스트 조성물에 관한 것으로, 특히 플루오르를 함유하는 감광성 폴리머 및 이를 포함하는 레지스트 조성물에 관한 것이다.The present invention relates to photosensitive polymers and chemically amplified resist compositions, and more particularly to photosensitive polymers containing fluorine and resist compositions comprising the same.
반도체 제조 공정이 복잡해지고 반도체 소자의 집적도가 증가함에 따라 미세한 패턴 형성이 요구된다. 더욱이, 반도체 소자의 용량이 1기가(Giga) 비트급 이상인 소자에 있어서, 디자인 룰이 0.1μm 이하인 패턴 사이즈가 요구되고, 그에 따라 기존의 KrF 엑시머 레이저(248nm)를 이용한 레지스트 재료를 사용하는 데 한계가 있다. 따라서, 새로운 에너지 노광원인 ArF 엑시머 레이저(193nm)를 이용한 리소그래피 기술이 등장하여 개발되었고 ArF 레지스트 조성물은 아크릴계 폴리머와, COMA (cycloolefin - maleic anhydride)계 두 가지가 중점적으로 연구되어 왔다.As the semiconductor manufacturing process becomes complicated and the degree of integration of semiconductor devices increases, fine pattern formation is required. Furthermore, in devices with a semiconductor device having a capacity of 1 gigabit or more, a pattern size of 0.1 μm or less is required, and thus there is a limit to using a resist material using a conventional KrF excimer laser (248 nm). have. Therefore, a lithography technique using ArF excimer laser (193 nm), which is a new energy exposure source, has been developed and developed. The ArF resist composition has been focused on acrylic polymer and COMA (cycloolefin-maleic anhydride).
최근, 패턴 사이즈를 더욱 줄이기 위하여 단파장을 발생시키는 F2(157nm) 엑시머 레이저를 이용하는 리소그래피에 대한 연구가 활발하다. 157nm의 단파장에서기존의 KrF 또는 ArF용 레지스트들을 사용하면 이들의 투과도가 매우 낮아 157nm용 레지스트로 사용하기에 적합하지 않다. 따라서, 157nm용 레지스트를 제조하기 위하여 157nm에서 투명한 새로운 구조의 고분자가 요구된다. 현상액(developer)에 용해가 가능한 화학 성분의 구조는 화학식 1에 나타낸 바와 같은 페놀(phenol), 카르복시산(carboxylic acid), α-플루오로카본 치환된 알콜 (α-fluorocarbon substituted alcohol) 또는 히드록시실란(hydroxy silane) 구조이다.Recently, research on lithography using an F 2 (157 nm) excimer laser that generates short wavelengths in order to further reduce the pattern size has been actively conducted. The use of existing KrF or ArF resists at short wavelengths of 157 nm is not very suitable for use as resists for 157 nm because their transmittance is very low. Therefore, a new polymer having a transparent structure at 157 nm is required to prepare a resist for 157 nm. The structure of the chemical component that can be dissolved in the developer is phenol, carboxylic acid, α-fluorocarbon substituted alcohol or hydroxysilane as shown in the formula (1). hydroxy silane) structure.
이 중에서 페놀과 카르복시산은 157nm에 대해 투과도가 현저히 낮다. 이에 반해 다른 두가지의 구조에 해당하는 α-플루오로카본 치환된 메탄올과 히드록시실란은 상대적으로 157nm 파장에 대해 높은 투과도를 나타내어 주 연구 대상이 되었다.Of these, phenol and carboxylic acid have a significantly low transmittance for 157 nm. In contrast, α-fluorocarbon-substituted methanol and hydroxysilane, which correspond to the other two structures, showed relatively high transmittances over a wavelength of 157 nm, and thus became a main research subject.
그러나, 최근의 연구에 따르면 페놀 및 카르복시산 유도체의 경우에도 플루오르를 적절히 치환시키면 투과율을 증가시킬 수 있고 콘트라스트(contrast) 증대에 효과적이기 때문에 157nm용 폴리머에 도입하고 있다.However, according to recent studies, phenol and carboxylic acid derivatives have been introduced into 157 nm polymers by appropriate substitution of fluorine to increase transmittance and to increase contrast.
에스테르기를 가짐에도 불구하고 아크릴레이트 구조가 높은 투과도를 가지고 손쉽게 얻어진다는 장점 때문에 이 구조에 적절히 플루오로카본을 치환시킨 구조를많이 이용함을 알 수 있다. 화학식 2에 그 구조를 예시하였다.Although it has an ester group, it can be seen that many of the structures in which a fluorocarbon is appropriately substituted for this structure have an advantage that the acrylate structure is easily obtained with high permeability. The structure is illustrated in Formula (2).
그 중에서 특히, t-부틸 트리플루오로메틸 아크릴레이트 (t-butyl trifluoromethyl acrylate)가 콘트라스트를 향상시키기 위한 모노머로 많이 이용된다. 157nm에서 투과도가 낮은 방향족 탄화수소계 모노머의 경우도 헥사플루오로이소프로판올 (hexafluoroisopropanol) 치환된 스티렌 (styrene) 구조로 바꾸어 줌으로써 투과도를 높여 레지스트로 사용될 수 있다. 화학식 3에 그 구조를 예시하였다.In particular, t-butyl trifluoromethyl acrylate is widely used as a monomer for improving contrast. Aromatic hydrocarbon monomers having low permeability at 157 nm can also be used as resists by increasing the transmittance by converting them into hexafluoroisopropanol substituted styrene structures. The structure is illustrated in the formula (3).
또한, 화학식 4에 나타낸 바와 같은 폴리(노르보르넨 술폰) 구조가 제안되었다.In addition, a poly (norbornene sulfone) structure as shown in formula (4) has been proposed.
이 구조는 COMA (cycloolefin - maleic anhydride)구조에 있어서 접착 프로모터(adhesion promoter)인 무수말레인산이 카르보닐기에 의해 157nm 파장 흡수가 일어나므로 이를 술폰(sulfone) 구조로 바꾸어 줌으로써 투과도 개선을 도모한 것이다.In this structure, maleic anhydride, which is an adhesion promoter, is absorbed at 157 nm by a carbonyl group in COMA (cycloolefin-maleic anhydride) structure, thereby improving transmittance by converting it into sulfone structure.
이 외에도 화학식 5에 나타낸 바와 같은 테트라플루오로에틸렌 (tetrafluoroethylene)과 노르보닐렌 (norbonylene) 유도체의 공중합체 구조를 가지는 레지스트에 대하여 활발히 연구되고 있으며, 화학식 6에 나타낸 바와 같이 폴리머의 주 사슬에 고리 에테르(cyclic ether) 형태의 구조가 도입된 구조 등에 대하여 연구되고 있다.In addition, there are active studies on resists having a copolymer structure of tetrafluoroethylene and norbornylene derivatives as shown in Formula 5, and ring ethers in the main chain of the polymer as shown in Formula 6. Structures in which a (cyclic ether) type structure is introduced have been studied.
본 발명의 목적은 레지스트 조성물의 원료로 사용되었을 때 F2(157nm) 엑시머 레이저 파장에 대하여 고투과율을 가지면서 하부 막질에 대하여 우수한 접착 특성을 제공할 수 있는 구조를 가지는 감광성 폴리머를 제공하는 것이다.It is an object of the present invention to provide a photosensitive polymer having a structure capable of providing excellent adhesion to the underlying film while having high transmittance with respect to the F 2 (157 nm) excimer laser wavelength when used as a raw material of a resist composition.
본 발명의 다른 목적은 F2(157nm) 엑시머 레이저 파장에 대하여 고투과율을 가지면서 하부 막질에 대한 접착 특성 및 친수성을 향상시킬 수 있는 레지스트 조성물을 제공하는 것이다.Another object of the present invention is to provide a resist composition having high transmittance with respect to the F 2 (157 nm) excimer laser wavelength and improving adhesion properties and hydrophilicity to the underlying film.
상기 목적을 달성하기 위하여, 본 발명에 따른 감광성 폴리머는 다음 구조의 반복 유니트를 포함한다.In order to achieve the above object, the photosensitive polymer according to the present invention includes a repeating unit of the following structure.
식중, R1은 1개 이상의 플루오르로 치환되거나 치환되지 않은 메틸기이고,R2는 1개 이상의 플루오르로 치환되거나 치환되지 않은 C1∼ C12의 탄화수소기이고, R1및 R2중 적어도 하나는 1개 이상의 플루오르로 치환된 기이다.Wherein R 1 is a methyl group unsubstituted or substituted with one or more fluorine, R 2 is a C 1 -C 12 hydrocarbon group unsubstituted or substituted with one or more fluorine, and at least one of R 1 and R 2 is Group substituted with one or more fluorine.
본 발명에 따른 감광성 폴리머는 다음중에서 선택되는 어느 하나의 구조를 가지는 반복 유니트를 포함할 수 있다.The photosensitive polymer according to the present invention may include a repeating unit having any one structure selected from the following.
상기 다른 목적을 달성하기 위하여, 본 발명의 제1 양태에 따른 레지스트 조성물은 다음 구조의 반복 유니트를 포함하는 감광성 폴리머와, PAG(photoacid generator)로 이루어진다.In order to achieve the above another object, the resist composition according to the first aspect of the present invention comprises a photosensitive polymer including a repeating unit having the following structure and a photoacid generator (PAG).
식중, R1및 R2는 상기 정의한 바와 같다.Wherein R 1 and R 2 are as defined above.
또한, 상기 다른 목적을 달성하기 위하여, 본 발명의 제2 양태에 따른 레지스트 조성물은 다음 구조의 제1 모노머 유니트와, 아크릴레이트 모노머, 메타크릴레이트 모노머, 무수 말레인산 모노머, 노르보르넨 모노머, 테트라플루오로에틸렌 및 이산화황으로 이루어지는 군에서 선택되는 적어도 하나의 제2 모노머 유니트와의 중합 생성물로 이루어지는 감광성 폴리머와, PAG로 이루어진다.In addition, in order to achieve the above another object, the resist composition according to the second aspect of the present invention comprises a first monomer unit having the following structure, an acrylate monomer, a methacrylate monomer, a maleic anhydride monomer, a norbornene monomer, and tetrafluoro It consists of a photosensitive polymer consisting of a polymerization product with at least one second monomer unit selected from the group consisting of ethylene and sulfur dioxide, and PAG.
식중, R1및 R2는 상기 정의한 바와 같다.Wherein R 1 and R 2 are as defined above.
본 발명의 제2 양태에 따른 레지스트 조성물에서, 상기 감광성 폴리머는 다음 구조를 포함할 수 있다.In the resist composition according to the second aspect of the present invention, the photosensitive polymer may include the following structure.
또한, 본 발명의 제2 양태에 따른 레지스트 조성물에서, 상기 감광성 폴리머는 다음 구조를 포함할 수 있다.In addition, in the resist composition according to the second aspect of the present invention, the photosensitive polymer may include the following structure.
또한, 본 발명의 제2 양태에 따른 레지스트 조성물에서, 상기 감광성 폴리머는 다음 구조를 포함할 수 있다.In addition, in the resist composition according to the second aspect of the present invention, the photosensitive polymer may include the following structure.
본 발명에 따른 레지스트 조성물에 있어서, 상기 감광성 폴리머의 중량 평균 분자량은 2,000 ∼ 100,000이다.In the resist composition which concerns on this invention, the weight average molecular weights of the said photosensitive polymer are 2,000-100,000.
상기 PAG는 상기 감광성 폴리머의 중량을 기준으로 1 ∼ 15 중량%의 양으로포함된다. 상기 PAG는 트리아릴술포늄염 (triarylsulfonium salts), 디아릴이오도늄염 (diaryliodonium salts), 술포네이트 (sulfonates) 또는 그 혼합물로 이루어질 수 있다.The PAG is included in an amount of 1 to 15% by weight based on the weight of the photosensitive polymer. The PAG may consist of triarylsulfonium salts, diaryliodonium salts, sulfonates or mixtures thereof.
본 발명에 따른 레지스트 조성물은 유기 염기를 더 포함할 수 있다. 상기 유기 염기는 상기 감광성 폴리머의 중량을 기준으로 0.01 ∼ 2.0 중량%의 양으로 포함된다.The resist composition according to the present invention may further comprise an organic base. The organic base is included in an amount of 0.01 to 2.0% by weight based on the weight of the photosensitive polymer.
본 발명에 따른 감광성 폴리머는 F2(157nm) 엑시머 레이저 파장에 대하여 고투과율을 가지며, 하부 막질에 대하여 우수한 접착 특성을 제공한다. 또한, 상기 감광성 폴리머로부터 얻어지는 본 발명에 따른 레지스트 조성물을 이용하여 미세한 라인 패턴을 형성할 때 감광성 폴리머의 백본에 도입된 피라닐 에테르 유도체에 의해 친수성이 향상되어 스웰링(swelling) 현상을 줄일 수 있으며, 염기성 수용액에서 현상이 잘 되어 미세한 패턴을 형성하는 데 유리하다.The photosensitive polymer according to the present invention has a high transmittance with respect to the F 2 (157 nm) excimer laser wavelength and provides excellent adhesion properties to the underlying film quality. In addition, when forming a fine line pattern using the resist composition according to the present invention obtained from the photosensitive polymer, the hydrophilicity is improved by the pyranyl ether derivative introduced into the backbone of the photosensitive polymer, thereby reducing the swelling phenomenon. It is well developed in basic aqueous solution, and is advantageous for forming a fine pattern.
다음에, 본 발명의 바람직한 실시예들에 대하여 상세히 설명한다.Next, preferred embodiments of the present invention will be described in detail.
합성예 1Synthesis Example 1
모노머의 합성Synthesis of Monomers
질소 조건 하에서 1,1,1,3,3,3-헥사플루오로-2-메틸-프로판-2-올 18g을 테트라히드로퓨란(THF) 100mL에 용해시킨 용액에 2.5 M 용액 n-부틸리튬 40mL를 0℃에서 적하하였다. 그 후, 2시간 동안 상온에서 교반하였다. 메타크릴로일 클로라이드 10.5g을 THF 50mL에 용해시킨 용액을 30분 동안 0℃에서 적하하였다. 상온에서 12시간 동안 교반한 후 에틸에테르 500mL와 증류수 300mL를 이용하여 추출하였다. 유기층은 MgSO4로 건조하고 에틸에테르를 감압하에서 제거한 후 분별증류하여 82%의 수율로 2-메틸-아크릴산 2,2,2-트리플루오로-1-메틸-1-트리플루오로메틸-에틸 에스테르를 얻었다.40 mL of 2.5 M solution n-butyllithium in a solution of 18 g of 1,1,1,3,3,3-hexafluoro-2-methyl-propan-2-ol dissolved in 100 mL of tetrahydrofuran (THF) under nitrogen conditions Was added dropwise at 0 ° C. Then, the mixture was stirred at room temperature for 2 hours. A solution of 10.5 g of methacryloyl chloride dissolved in 50 mL of THF was added dropwise at 0 ° C. for 30 minutes. After stirring at room temperature for 12 hours, the mixture was extracted using 500 mL of ethyl ether and 300 mL of distilled water. The organic layer was dried over MgSO 4 , ethyl ether was removed under reduced pressure, and then distilled separately to give 2-methyl-acrylic acid 2,2,2-trifluoro-1-methyl-1-trifluoromethyl-ethyl ester in a yield of 82%. Got.
합성예 2Synthesis Example 2
모노머의 합성Synthesis of Monomers
합성예 1에서와 동일한 방법으로 1,1,1,3,3,3-헥사플루오로-프로판-2-올을 이용하여 79%의 수율로 2-메틸-아크릴산 2,2,2-트리플루오로-1-트리플루오로메틸-에틸 에스테르를 합성할 수 있었다.2-methyl-acrylic acid 2,2,2-trifluoro in a yield of 79% using 1,1,1,3,3,3,3-hexafluoro-propan-2-ol in the same manner as in Synthesis example 1 Rho-1-trifluoromethyl-ethyl ester could be synthesized.
합성예 3Synthesis Example 3
모노머의 합성Synthesis of Monomers
합성예 1에서와 동일한 방법으로 1,1,2,2,2-펜타플루오로-에탄올을 이용하여 84%의 수율로 2-메틸-아크릴산 2,2,3,3,3-펜타플루오로-프로필 에스테르를 합성할 수 있었다.2-Methyl-acrylic acid 2,2,3,3,3-pentafluoro- in a yield of 84% using 1,1,2,2,2-pentafluoro-ethanol in the same manner as in Synthesis example 1 The propyl ester could be synthesized.
합성예 4Synthesis Example 4
모노머의 합성Synthesis of Monomers
2-메틸-아크릴산 2,2,2-트리플루오로-1-메틸-1-트리플루오로메틸-에틸 에스테르 30g과 아크롤레인 6.7g을 100mL 스테인레스 스틸 봄베(bomb)에 넣고 170℃에서 10시간 동안 교반하였다. 반응 후, 분별증류하여 52%의 수율로 2-메틸-3,4-디히드로-2H-피란-2-카르복시산 2,2,2-트리플루오로-1-메틸-1-트리플루오로메틸-에틸 에스테르를 얻었다.30 g of 2-methyl-acrylic acid 2,2,2-trifluoro-1-methyl-1-trifluoromethyl-ethyl ester and 6.7 g of acrolein were placed in a 100 mL stainless steel bomb and stirred at 170 ° C. for 10 hours. It was. After reaction, fractional distillation to yield 2-methyl-3,4-dihydro-2H-pyran-2-carboxylic acid 2,2,2-trifluoro-1-methyl-1-trifluoromethyl- in 52% yield. Ethyl ester was obtained.
합성예 5Synthesis Example 5
모노머의 합성Synthesis of Monomers
합성예 1에서와 동일한 방법으로 2-메틸-아크릴산 2,2,2-트리플루오로-1-트리플루오로메틸-에틸 에스테르를 이용하여 64%의 수율로 2-메틸-3,4-디히드로-2H-피란-2-카르복시산 2,2,2-트리플루오로-1-트리플루오로메틸-에틸 에스테르를 합성할 수 있었다.2-methyl-3,4-dihydro in the yield of 64% using 2-methyl-acrylic acid 2,2,2-trifluoro-1-trifluoromethyl-ethyl ester in the same manner as in Synthesis example 1 -2H-pyran-2-carboxylic acid 2,2,2-trifluoro-1-trifluoromethyl-ethyl ester could be synthesized.
합성예 6Synthesis Example 6
모노머의 합성Synthesis of Monomers
합성예 5에서와 동일한 방법으로 2-메틸-아크릴산 2,2,3,3,3-펜타플루오로-프로필 에스테르를 이용하여 67%의 수율로 2-메틸-3,4-디히드로-2H-피란-2-카르복시산 2,2,3,3,3-펜타플루오로-프로필 에스테르를 합성할 수 있었다.2-methyl-3,4-dihydro-2H- in a yield of 67% using 2-methyl-acrylic acid 2,2,3,3,3-pentafluoro-propyl ester in the same manner as in Synthesis example 5. Pyran-2-carboxylic acid 2,2,3,3,3-pentafluoro-propyl ester could be synthesized.
실시예 1Example 1
폴리머의 합성Synthesis of Polymer
2-메틸-3,4-디히드로-2H-피란-2-카르복시산 2,2,2-트리플루오로-1-메틸-1-트리플루오로메틸-에틸 에스테르 3.1g과, 2-트리플루오로메틸-아크릴산 t-부틸 에스테르 2g, 1,1,1,3,3,3-헥사플루오로-2-(4-비닐-페닐)-프로판-2-올 5.4g과, AIBN (azobisisobutyronitrile) 0.33g을 65℃에서 24시간 반응시킨 후 헥산에 재침전하여 상기 폴리머를 회수하였다. (수율 62%)3.1 g of 2-methyl-3,4-dihydro-2H-pyran-2-carboxylic acid 2,2,2-trifluoro-1-methyl-1-trifluoromethyl-ethyl ester and 2-trifluoro 2 g of methyl-acrylic acid t-butyl ester, 5.4 g of 1,1,1,3,3,3-hexafluoro-2- (4-vinyl-phenyl) -propan-2-ol, and 0.33 g of AIBN (azobisisobutyronitrile) The reaction was carried out at 65 ° C. for 24 hours and then reprecipitated in hexane to recover the polymer. (Yield 62%)
이 때, 얻어진 생성물의 중량 평균 분자(Mw)량은 12,600이었고, 다분산도(Mw/Mn)는 2.2이었다.At this time, the weight average molecular weight (Mw) of the obtained product was 12,600, and polydispersity (Mw / Mn) was 2.2.
실시예 2Example 2
폴리머의 합성Synthesis of Polymer
2-메틸-3,4-디히드로-2H-피란-2-카르복시산 2,2,2-트리플루오로-1-메틸-1-트리플루오로메틸-에틸 에스테르 2.9g과, 2-트리플루오로메틸-아크릴산 t-부틸 에스테르 2g과, 1,1,1,3,3,3-헥사플루오로-2-(4-비닐-페닐)-프로판-2-올 5.4g과 AIBN 0.33g을 65℃에서 24시간 반응시킨 후, 헥산에 재침전하여 상기 폴리머를 회수하였다. (수율 64%)2.9 g of 2-methyl-3,4-dihydro-2H-pyran-2-carboxylic acid 2,2,2-trifluoro-1-methyl-1-trifluoromethyl-ethyl ester and 2-trifluoro 65 g of 2 g of methyl-acrylic acid t-butyl ester, 5.4 g of 1,1,1,3,3,3-hexafluoro-2- (4-vinyl-phenyl) -propan-2-ol and 0.33 g of AIBN After reacting for 24 hours at, the precipitate was reprecipitated in hexane to recover the polymer. (64% yield)
이 때, 얻어진 생성물의 중량 평균 분자(Mw)량은 14,300이었고, 다분산도(Mw/Mn)는 2.2이었다.At this time, the weight average molecular weight (Mw) of the obtained product was 14,300, and polydispersity (Mw / Mn) was 2.2.
실시예 3Example 3
폴리머의 합성Synthesis of Polymer
2-메틸-3,4-디히드로-2H-피란-2-카르복시산 2,2,3,3,3-펜타플루오로-프로필 에스테르 2.7g과, 2-트리플루오로메틸-아크릴산 t-부틸 에스테르 2g과, 1,1,1,3,3,3-헥사플루오로-2-(4-비닐-페닐)-프로판-2-올 5.4g과, AIBN 0.33g을 65℃에서 24시간 반응시킨 후, 헥산에 재침전하여 상기 폴리머를 회수하였다. (수율 64%)2.7 g of 2-methyl-3,4-dihydro-2H-pyran-2-carboxylic acid 2,2,3,3,3-pentafluoro-propyl ester and 2-trifluoromethyl-acrylic acid t-butyl ester 2 g, 1,1,1,3,3,3-hexafluoro-2- (4-vinyl-phenyl) -propan-2-ol and 5.4 g of AIBN 0.33 g were reacted at 65 ° C. for 24 hours. The polymer was recovered by reprecipitation in hexane. (64% yield)
실시예 4Example 4
레지스트 조성물의 제조Preparation of Resist Composition
실시예 1, 실시예 2 및 실시예 3에서 얻어진 폴리머 (0.5g)들을 각각 PAG(photoacid generator)인 트리페닐술포늄 트리플루오로메탄술포네이트(트리플레이트) (0.005g) 및 유기 염기인 트리이소데실아민 (1.6mg)과 함께, 시클로헥사논 (10g)의 혼합 용액에 넣어 완전히 녹인 후, 각각 0.2μm 멤브레인 필터를 이용하여 걸러서 각각의 레지스트 조성물들을 얻었다. 이들 레지스트 조성물을 유기 ARC(Anti-Reflective Coating) 처리된 Si 웨이퍼상에 각각 약 0.1 ㎛의 두께로 코팅하였다.The polymers (0.5 g) obtained in Examples 1, 2 and 3 were respectively triphenylsulfonium trifluoromethanesulfonate (triplate) (0.005 g) which is a photoacid generator (PAG) and triiso which is an organic base. Into a mixed solution of cyclohexanone (10 g) with decylamine (1.6 mg) was completely dissolved, and then filtered using a 0.2 μm membrane filter respectively to obtain respective resist compositions. These resist compositions were coated on organic Anti-Reflective Coating (ARC) treated Si wafers each about 0.1 μm thick.
그 후, 상기 레지스트 조성물이 코팅된 각각의 웨이퍼를 120℃의 온도에서 90초 동안 소프트 베이킹하고, F2엑시머 레이저 스테퍼(NA = 0.6)를 이용하여 노광한 후, 120℃의 온도에서 60초 동안 PEB를 실시하였다.Thereafter, each wafer coated with the resist composition was soft baked at a temperature of 120 ° C. for 90 seconds, exposed using an F 2 excimer laser stepper (NA = 0.6), and then 60 seconds at a temperature of 120 ° C. PEB was performed.
그 후, 2.38 중량% TMAH(tetramethylammonium hydroxide) 용액을 사용하여 약 30 ∼ 60초 동안 현상하여 레지스트 패턴을 형성하였다.Thereafter, using a 2.38% by weight tetramethylammonium hydroxide (TMAH) solution, development was performed for about 30 to 60 seconds to form a resist pattern.
그 결과, 노광 도즈량을 약 5 ∼ 30 mJ/cm2으로 하였을 때 0.10 ∼ 0.20 ㎛ 라인 앤드 스페이스 패턴(lines and spaces pattern)이 얻어지는 것을 확인하였다.As a result, when the exposure dose amount was set to about 5 to 30 mJ / cm 2 , it was confirmed that 0.10 to 0.20 μm line and spaces pattern was obtained.
본 발명에서는 F2(157nm) 엑시머 레이저 파장에 대하여 고투과율을 가지는 레지스트 조성물을 제공하기 위하여 백본에 피라닐 에테르 구조가 도입된 감광성 폴리머를 제공한다. 따라서, 본 발명에 따른 감광성 폴리머는 하부 막질에 대하여 우수한 접착 특성을 제공한다. 또한, 폴리머의 백본에 포함된 피라닐 에테르 유도체는 친수성이 매우 크다. 따라서, 상기 감광성 폴리머로부터 얻어지는 본 발명에 따른 레지스트 조성물을 이용하여 미세한 라인 패턴을 형성할 때 스웰링(swelling) 현상을 줄일 수 있으며, 염기성 수용액에서 현상이 잘 되어 미세한 패턴을 형성하는 데 유리하다. 따라서, 본 발명에 따른 레지스트 조성물을 F2(157nm) 엑시머 레이저를 이용하는 포토리소그래피 공정에 적용할 때 우수한 리소그래피 퍼포먼스를 나타냄으로써, 향후 차세대 반도체 소자를 제조하는 데 있어서 매우 유용하게 사용될 수 있다.The present invention provides a photosensitive polymer having a pyranyl ether structure introduced into the backbone to provide a resist composition having a high transmittance with respect to the F 2 (157 nm) excimer laser wavelength. Thus, the photosensitive polymer according to the present invention provides excellent adhesion properties to the underlying film quality. In addition, pyranyl ether derivatives contained in the backbone of the polymer are very hydrophilic. Therefore, the swelling phenomenon can be reduced when forming a fine line pattern using the resist composition according to the present invention obtained from the photosensitive polymer, and is well developed in a basic aqueous solution, which is advantageous for forming a fine pattern. Thus, when the resist composition according to the present invention is applied to a photolithography process using an F 2 (157 nm) excimer laser, it exhibits excellent lithography performance, which can be very useful for manufacturing future next-generation semiconductor devices.
이상, 본 발명을 바람직한 실시예를 들어 상세하게 설명하였으나, 본 발명은 상기 실시예에 한정되지 않고, 본 발명의 기술적 사상의 범위 내에서 당 분야에서 통상의 지식을 가진 자에 의하여 여러가지 변형이 가능하다.The present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. Do.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020070854A (en) * | 2001-02-28 | 2002-09-11 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Polymers, resist compositions and patterning process |
| KR100442865B1 (en) * | 2001-11-07 | 2004-08-02 | 삼성전자주식회사 | Photosensitive polymer having fluorinated ethylene glycol group and chemically amplified resist composition comprising the same |
| KR100475076B1 (en) * | 2002-05-28 | 2005-03-10 | 삼성전자주식회사 | Photosensitive polymer including fluorine and resist composition containing the same |
| CN108333866A (en) * | 2016-11-29 | 2018-07-27 | 台湾积体电路制造股份有限公司 | The method of lithographic patterning |
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2001
- 2001-09-10 KR KR1020010055469A patent/KR20030021907A/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020070854A (en) * | 2001-02-28 | 2002-09-11 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Polymers, resist compositions and patterning process |
| KR100442865B1 (en) * | 2001-11-07 | 2004-08-02 | 삼성전자주식회사 | Photosensitive polymer having fluorinated ethylene glycol group and chemically amplified resist composition comprising the same |
| KR100475076B1 (en) * | 2002-05-28 | 2005-03-10 | 삼성전자주식회사 | Photosensitive polymer including fluorine and resist composition containing the same |
| CN108333866A (en) * | 2016-11-29 | 2018-07-27 | 台湾积体电路制造股份有限公司 | The method of lithographic patterning |
| CN108333866B (en) * | 2016-11-29 | 2022-09-30 | 台湾积体电路制造股份有限公司 | Method of photolithographic patterning |
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