KR20070072738A - Monomer, polymer for photoresist and photoresist composition comprising same - Google Patents
Monomer, polymer for photoresist and photoresist composition comprising same Download PDFInfo
- Publication number
- KR20070072738A KR20070072738A KR1020060000189A KR20060000189A KR20070072738A KR 20070072738 A KR20070072738 A KR 20070072738A KR 1020060000189 A KR1020060000189 A KR 1020060000189A KR 20060000189 A KR20060000189 A KR 20060000189A KR 20070072738 A KR20070072738 A KR 20070072738A
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- KR
- South Korea
- Prior art keywords
- formula
- photoresist
- mol
- polymer
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 114
- 239000000178 monomer Substances 0.000 title claims abstract description 53
- 229920000642 polymer Polymers 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 62
- -1 norbornene dihydropyrrole compound Chemical class 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
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- 238000000206 photolithography Methods 0.000 abstract description 6
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- DCTVCFJTKSQXED-UHFFFAOYSA-N (2-ethyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(CC)(OC(=O)C(C)=C)C2C3 DCTVCFJTKSQXED-UHFFFAOYSA-N 0.000 description 6
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- 230000002829 reductive effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
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- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 4
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- 230000018109 developmental process Effects 0.000 description 2
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- 150000002118 epoxides Chemical class 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
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- WBUSZOLVSDXDOC-UHFFFAOYSA-M (4-methoxyphenyl)-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(OC)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WBUSZOLVSDXDOC-UHFFFAOYSA-M 0.000 description 1
- AWOATHYNVXCSGP-UHFFFAOYSA-M (4-methylphenyl)-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 AWOATHYNVXCSGP-UHFFFAOYSA-M 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/72—4,7-Endo-alkylene-iso-indoles
-
- 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
- G03F7/039—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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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Abstract
248nm 및 193nm 이하의 단파장의 노광원을 사용하는 포토리소그라피 공정에서 라인에지러프니스를 줄이고, 노광 후 선폭크기의 변화를 줄일 수 있는 노보넨 디히드로피롤계 포토레지스트용 모노머, 폴리머 및 이를 포함하는 포토레지스트 조성물이 개시된다. 상기 포토레지스트용 모노머는 하기 화학식 1로 표시된다.Monomers and polymers for norbornene dihydropyrrole-based photoresists that can reduce line edge roughness and reduce line width after exposure in photolithography processes using short-source exposure sources of less than 248 nm and 193 nm A resist composition is disclosed. The photoresist monomer is represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서, 상기 R은 수소 또는 메틸기이다.In Formula 1, R is hydrogen or a methyl group.
Description
도 1은 본 발명의 실시예에 따른 포토레지스트용 고분자의 최적노광량(EOP) 변화를 나타낸 그래프.1 is a graph showing a change in the optimum exposure amount (EOP) of the photoresist polymer according to an embodiment of the present invention.
도 2는 본 발명의 실시예에 따른 포토레지스트용 고분자의 노광 후 가열(PEB) 온도에 따른 100nm 패턴의 선폭크기 변화를 나타낸 그래프.Figure 2 is a graph showing the change in line width of the 100nm pattern according to the post-exposure heating (PEB) temperature of the photoresist polymer according to an embodiment of the present invention.
본 발명은 포토레지스트용 모노머, 폴리머 및 이를 포함하는 포토레지스트 조성물에 관한 것으로서, 더욱 상세하게는 248nm 및 193nm 이하의 단파장의 노광원을 사용하는 포토리소그라피 공정에서 라인에지러프니스를 줄이고, 노광 후 선폭크기의 변화를 줄일 수 있는 노보넨 디히드로피롤계 포토레지스트용 모노머, 폴리머 및 이를 포함하는 포토레지스트 조성물에 관한 것이다.The present invention relates to a photoresist monomer, a polymer and a photoresist composition comprising the same, and more particularly, to reduce line edge roughness in a photolithography process using a short wavelength source of 248 nm and 193 nm or less, and to expose line width after exposure. The present invention relates to a monomer for a norbornene dihydropyrrole-based photoresist, a polymer, and a photoresist composition including the same, which can reduce a change in size.
최근, 반도체 소자의 고집적화에 따라, 기가비트(Gigabit)급 이상의 기억용량을 갖는 다이나믹 랜덤 액서스 메모리(DRAM)의 개발이 활발히 진행되고 있다. 1기가 비트급 이상의 DRAM을 제조하기 위해서는, 100nm 이하의 선폭을 갖는 극미세 패턴을 형성하여야 한다. 이를 위하여, g-라인(436nm), i-라인(365nm)보다 KrF 엑시머 레이저(248nm) 또는 더욱 단파장인 ArF 엑시머 레이저(193nm) 이하를 노광원으로 사용하는 포토리소그래피 기술이 도입되었으며, 단파장의 노광원에서 고해상력을 가질 뿐만 아니라, 투명성, 건식 식각(dry etching) 내성, 하부 막질에 대한 접착성, 현상성 등이 우수한 포토레지스트 조성물에 대한 연구가 활발히 진행되고 있다. 특히 패턴이 미세화될수록, 포토 및 식각 공정 마진을 감소시켜야 하므로, 레지스트 조성물의 투명성 향상, 라인에지 러프니스(line edge roughness)의 감소, 노광 후 가열(Post Exposure Bake: PEB) 온도에 따른 선폭 변화 감소 등의 중요성이 더욱 증대되고 있다. Recently, with the high integration of semiconductor devices, the development of dynamic random access memory (DRAM) having a storage capacity of more than a gigabit level has been actively progressed. In order to manufacture DRAM of 1 gigabit or more, an ultrafine pattern having a line width of 100 nm or less must be formed. To this end, photolithography technology using KrF excimer laser (248 nm) or shorter ArF excimer laser (193 nm) or less than g-line (436 nm) or i-line (365 nm) as an exposure source has been introduced. In addition to the high resolution in the circle, research on the photoresist composition excellent in transparency, dry etching resistance, adhesion to the underlying film, developability and the like are being actively conducted. In particular, as the pattern becomes finer, the photo and etching process margins must be reduced, thereby improving the transparency of the resist composition, reducing line edge roughness, and decreasing line width variations due to post exposure bake (PEB) temperature. The importance of the back is increasing.
일반적으로 ArF 엑시머 레이저용 포토레지스트 조성물은 193nm 파장에서의 투명성, 건식 식각 내성 및 하부 막질에 대한 접착성이 높아야 하며, 현상액으로 널리 사용되는 2.38중량% 테트라메틸암모늄 히드록사이드(TMAH) 수용액에서 현상이 용이해야 한다. 특히 패턴이 미세화 될수록 레지스트 조성물의 투명성 향상과 라인 에지 러프니스의 감소가 강조되고 있으며, PEB에 따른 선폭변화의 크기의 중요성이 더욱 증대되고 있다. 포토 공정시 더 작은 선폭변화를 유지해야만 최종적으로 형성 되는 미세패턴의 크기를 유지할 수 있기 때문이다. 따라서 미세패턴 포토공정에서 레지스트가 갖추어야 할 가장 큰 조건은 라인 에지 러프니스 감소 및 PEB온도에 따른 낮은 선폭변화의 크기이다. In general, the photoresist composition for ArF excimer laser should have high transparency at 193nm, dry etching resistance and high adhesion to the underlying film, and develop in 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution widely used as developer. This should be easy. In particular, as the pattern becomes finer, the transparency of the resist composition and the decrease of the line edge roughness are emphasized, and the importance of the size of the line width change according to the PEB is further increased. This is because the size of the final fine pattern can be maintained only by maintaining a smaller line width change during the photo process. Therefore, in the fine pattern photo process, the biggest requirement for the resist is to reduce the line edge roughness and the size of the low line width change according to the PEB temperature.
따라서, 본 발명의 목적은 라인에지러프니스를 줄이고, 노광 후, 온도 증가에 따른 패턴의 선폭 변화를 감소시킬 수 있는 포토레지스트용 모노머, 폴리머 및 이를 포함하는 포토레지스트 조성물을 제공하는 것이다. Accordingly, it is an object of the present invention to provide a photoresist monomer, a polymer, and a photoresist composition including the same, which can reduce line edge roughness and reduce the line width change of a pattern with an increase in temperature after exposure.
본 발명의 다른 목적은 고해상도, 높은 건식 식각 안정성 및 넓은 공정여유도를 갖는 포토레지스트용 모노머, 폴리머 및 이를 포함하는 포토레지스트 조성물을 제공하는 것이다. Another object of the present invention is to provide a photoresist monomer, a polymer, and a photoresist composition comprising the same, having a high resolution, high dry etching stability, and a wide processing margin.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 모노머를 제공한다. In order to achieve the above object, the present invention provides a monomer represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서, 상기 R은 수소 또는 메틸기이다.In Formula 1, R is hydrogen or a methyl group.
또한, 본 발명은 하기 화학식 2로 표시되는 반복단위를 포함하는 포토레지스트용 폴리머를 제공한다.The present invention also provides a photoresist polymer comprising a repeating unit represented by the following formula (2).
[화학식 2] [Formula 2]
상기 화학식 2에서, 상기 R은 수소 또는 메틸기이다.In Formula 2, R is hydrogen or a methyl group.
또한 본 발명은 상기 포토레지스트용 폴리머를 포함하는 포토레지스트 조성물 및 상기 포토레지스트 조성물을 사용한 포토레지스트 패턴의 형성방법을 제공한다.The present invention also provides a photoresist composition comprising the photoresist polymer and a method of forming a photoresist pattern using the photoresist composition.
이하, 첨부된 도면을 참조하여 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.
본 발명에 따른 포토레지스트용 모노머는 하기 화학식 1로 표시된다. The monomer for photoresists according to the present invention is represented by the following formula (1).
상기 화학식 1에서, 상기 R은 수소 또는 메틸기이다.In Formula 1, R is hydrogen or a methyl group.
본 발명에 따른 상기 화학식 1로 표시되는 염기성 포토레지스트용 모노머는 하기 반응식 1과 같이 사이클로펜타디엔과 디히드로피롤의 디엘스-알더반응으로 생성된 노보넨 디히드로피롤계 화합물(A)에 과산화물(peroxide)을 첨가하여, 노보넨의 이중 결합을 산화시켜 에폭시드(epoxide) 화합물(B)로 만들고, 산성 조건하에서 물, 알코올, 티올 등을 첨가하여, 개환 부가 반응시킴으로써, 하이드록실기를 가진 노보넨 디히드로피롤계 화합물(C)을 얻은 후, (메타)아크릴로일 클로라이드와 1 내지 12 시간 동안 테트라히드로퓨란(THF) 등의 통상적인 유기용매 중에서 반응시켜 얻을 수 있다. The monomer for a basic photoresist represented by the formula (1) according to the present invention is a peroxide (A) in the norbornene dihydropyrrole compound (A) produced by the Diels-Alder reaction of cyclopentadiene and dihydropyrrole as shown in
상기 반응식 1에서 R은 수소 또는 메틸기이다.In
본 발명은 하기 화학식 2로 표시되는 반복단위를 포함하는 포토레지스트용 폴리머를 제공한다.The present invention provides a photoresist polymer comprising a repeating unit represented by the following formula (2).
상기 화학식 2에서, 상기 R은 수소 또는 메틸기이다.In Formula 2, R is hydrogen or a methyl group.
상기 화학식 2로 표시되는 반복단위와 함께 중합될 수 있는 모노머로는 포토레지스트용 폴리머 제조에 통상적으로 사용되는 모노머를 사용할 수 있으며, 예를 들면 하기 화학식 3 및 화학식 4로 표시되는 모노머를 예시할 수 있다.As a monomer that can be polymerized with the repeating unit represented by Formula 2, a monomer commonly used in preparing a photoresist polymer may be used, and examples thereof include monomers represented by
상기 화학식 3에서, R은 수소 또는 메틸기이고, R1은 산에 민감한 보호기로서, 탄소수 1 내지 20의 알킬 또는 탄소수 1 내지 40의 사이클로알킬기이다.In Formula 3, R is hydrogen or a methyl group, R 1 is an acid-sensitive protecting group, an alkyl having 1 to 20 carbon atoms or a cycloalkyl group having 1 to 40 carbon atoms.
상기 화학식 4에서, R은 수소 또는 메틸기이고, R2는 탄소수 1 내지 20의 히드록시알킬기, 에테르기 또는 에스테르기를 포함하는 탄소수 5 내지 10의 사이클로알킬 또는 사이클로락톤기이다.In Formula 4, R is hydrogen or a methyl group, R 2 is a cycloalkyl or cyclolactone group having 5 to 10 carbon atoms including a hydroxyalkyl group, ether group or ester group having 1 to 20 carbon atoms.
따라서 본 발명에 따른, 포토레지스트용 폴리머의 바람직한 예는 하기 화학식 5로 표시되는 폴리머이며, 더욱 바람직한 예는 하기 화학식 5a 내지 5h로 표시되는 폴리머이다.Therefore, according to the present invention, a preferred example of the photoresist polymer is a polymer represented by the following formula (5), and a more preferred example is a polymer represented by the following formulas (5a to 5h).
상기 화학식 5에서, R은 각각 독립적으로 수소 또는 메틸기이고, R1은 탄소수 1 내지 20의 알킬 또는 탄소수 1 내지 40의 사이클로알킬기이며, R2는 각각 독립적으로 탄소수 1 내지 20의 히드록시알킬기, 에테르기 또는 에스테르기를 포함하는 탄소수 5 내지 10의 사이클로알킬 또는 사이클로락톤기이고, a, b, c, 및 d는 상기 폴리머 사슬을 구성하는 반복단위의 몰%로서, 각각 1~60몰%, 1~60몰%, 1~60몰%, 및 1~60몰%이다.In Formula 5, R is each independently hydrogen or a methyl group, R 1 is an alkyl having 1 to 20 carbon atoms or a cycloalkyl group having 1 to 40 carbon atoms, R 2 are each independently a hydroxyalkyl group having 1 to 20 carbon atoms, ether A cycloalkyl or cyclolactone group having 5 to 10 carbon atoms including a group or an ester group, and a, b, c, and d are mole% of the repeating units constituting the polymer chain, and are 1 to 60 mole% and 1 to 1, respectively. 60 mol%, 1-60 mol%, and 1-60 mol%.
상기 화학식 5a 내지 5h에서, R, a, b, c, 및 d는 상기 화학식 5에서 정의한 바와 같다.In Formulas 5a to 5h, R, a, b, c, and d are as defined in Formula 5.
본 발명에 따른 포토레지스트용 폴리머는 블록 공중합체 또는 랜덤 공중합체일 수 있으며, 중량평균분자량(Mw)은 3,000 내지 100,000이고, 다분산도(Polydispersity)는 1.0 내지 5.0인 것이 바람직하다. 상기 중량평균분자량, 분산도가 상기 범위를 벗어나면, 포토레지스트막의 물성이 저하되거나, 포토레지스트막의 형성이 곤란하고, 패턴의 콘트라스트가 저하될 우려가 있다. 본 발명에 따른, 포토레지스트용 폴리머의 측쇄에 붙어있는, 노보넨 디히드로피롤계 모노머는 상기 폴리머 및 이를 포함한 포토레지스트 조성물이 노광부의 광산발생제에서 생긴 산 촉매(H+)를 레지스트 내에서 염기로 작용하여 산 확산을 조절한다. 일반적으로 화학증폭형 레지스트(CAR; Chemical Amplified Resist) 형태의 ArF 레지스트를 이용한 포토리소그라피 공정에 있어서, 노광된 포토레지스트에 존재하는 산(acid) 성분을 활성화 및 확산시키기 위하여, 노광 후 가열(PEB) 공정을 수행하는데, 이때 가열온도가 높으면 산의 확산이 원활이 이루어져 가열된 산 성분이 비노광부의 포토 레지스트에 침투하여, 비노광부의 용해도까지 증가시킴으로서, 포토레지스트 패턴의 선폭을 변화시키거나, 패턴의 무너짐, 라인에지 러프니스 등을 유발시킨다. 따라서 상기 화학식 2로 표시되는 반복단위를 포함하는 포토레지스트용 폴리머는 상기 폴리머 사슬내의 노보넨 디히드로피롤계 화합물이 산 확산을 조절할 수 있기 때문에, 가열온도의 변화에 민감하지 않고, 결국 산 확산 정도를 감소시킬 수 있어 노광 후 선폭변화를 줄일 수 있다.The photoresist polymer according to the present invention may be a block copolymer or a random copolymer, and the weight average molecular weight (Mw) is 3,000 to 100,000, and the polydispersity is preferably 1.0 to 5.0. When the weight average molecular weight and the dispersion degree are outside the above ranges, the physical properties of the photoresist film may be lowered, or the formation of the photoresist film may be difficult, and the contrast of the pattern may be lowered. The norbornene dihydropyrrole monomer, which is attached to the side chain of the polymer for photoresist, according to the present invention, is characterized in that the polymer and the photoresist composition including the same are based on the acid catalyst (H + ) generated in the photoacid generator of the exposed part. To regulate acid diffusion. Generally, in photolithography process using ArF resist in the form of Chemical Amplified Resist (CAR), post-exposure heating (PEB) to activate and diffuse an acid component present in the exposed photoresist. In this case, when the heating temperature is high, acid diffuses smoothly, and the heated acid component penetrates into the photoresist of the non-exposed part and increases the solubility of the non-exposed part, thereby changing the line width of the photoresist pattern, or This can cause a collapse, line edge roughness, etc. Therefore, the photoresist polymer including the repeating unit represented by Formula 2 is not sensitive to the change in heating temperature because the norbornene dihydropyrrole compound in the polymer chain can control acid diffusion, and thus the degree of acid diffusion. It can reduce the line width change can be reduced after exposure.
본 발명에 따른, 상기 포토레지스트용 폴리머는, a)상기 화학식 1로 표시되는 모노머, 필요에 따라 다른 모노머 및 중합 개시제를 중합용매에 용해시키고, b)상기 혼합물 용액을 질소, 아르곤 등의 불활성 분위기하에서, 30 내지 70℃ 온도에서 4 내지 24 시간 동안 반응시켜서 제조할 수 있다. 또한, 상기 중합반응은 라디칼 중합 반응, 용액 중합 반응, 벌크 중합 반응 또는 금속 촉매를 이용한 중합 반응으로 수행될 수 있다. 또한 상기 제조 방법은 상기 (b) 반응 결과물을 디에틸에테르, 석유에테르 (petroleum ether), 메탄올, 에탄올 또는 이소프로판올을 포함하는 저급 알코올, 물, 이들의 혼합물 등을 사용하여 정제하는 단계를 더욱 포함할 수도 있다. 상기 중합용매로는 당업계에서 통상적으로 알려진 중합용매를 광범위하게 사용할 수 있고, 비한정적으로는 사이클로헥사논, 사이클로펜타논, 테트라히드로푸란, 디메틸포름아미드, 디메틸설폭사이드, 디옥산, 메틸에틸케톤, 벤젠, 톨루엔, 자일렌, 또는 이들의 혼합물을 예시할 수 있으며, 상기 중합개시제 역시 당업계에서 통상적으로 알려진 중합개시제를 광범위하게 사용할 수 있고, 비한정적으로 는 벤조일퍼옥사이드, 2,2'-아조비스이소부티로니트릴 (AIBN), 아세틸퍼옥사이드, 라우릴퍼옥사이드, t-부틸퍼아세테이트, t-부틸하이드로퍼옥사이드, 디-t-부틸퍼옥사이드 또는 이들의 혼합물을 예시할 수 있다. 예를 들면, 상기 화학식 1로 표시되는 모노머 및 상기 화학식 3 및 4로 표시되는 모노머를 하기 반응식 2와 같이 중합하여, 상기 화학식 5로 표시되는 포토레지스트용 폴리머를 제조할 수 있다. The photoresist polymer according to the present invention comprises a) dissolving the monomer represented by the formula (1), if necessary, another monomer and a polymerization initiator in a polymerization solvent, and b) an inert atmosphere such as nitrogen and argon. Under reaction at a temperature of 30 to 70 ° C. for 4 to 24 hours. In addition, the polymerization may be performed by a radical polymerization reaction, a solution polymerization reaction, a bulk polymerization reaction or a polymerization reaction using a metal catalyst. In addition, the preparation method may further comprise the step of (b) purifying the reaction product using a lower alcohol, water, a mixture thereof, and the like, including diethyl ether, petroleum ether, methanol, ethanol or isopropanol. It may be. As the polymerization solvent, a polymerization solvent commonly known in the art may be widely used, but is not limited to cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, methyl ethyl ketone , Benzene, toluene, xylene, or a mixture thereof may be exemplified, and the polymerization initiator may also be widely used as polymerization initiators commonly known in the art, but are not limited to benzoyl peroxide, 2,2′- Azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide, t-butylperacetate, t-butylhydroperoxide, di-t-butylperoxide or mixtures thereof. For example, the monomer represented by Chemical Formula 1 and the monomers represented by Chemical Formulas 3 and 4 may be polymerized as in
상기 반응식 2에서, R, R1, R2, a, b, c, 및 d는 상기 화학식 5에서 정의한 바와 같다.In
본 발명에 따른 포토레지스트 조성물은, 상기 화학식 2로 표시되는 반복 단위를 포함하는 포토레지스트용 폴리머, 산을 발생시키는 광산 발생제 및 유기 용매를 포함하며, 필요에 따라 각종 첨가제를 더욱 포함할 수 있다. 상기 화학식 2로 표시되는 반복 단위를 포함하는 포토레지스트용 폴리머의 함량은 전체 포토레지스트 조성물에 대하여 1 내지 30중량%인 것이 바람직하다. 만일 상기 포토레지스트용 폴리머의 함량이 1중량% 미만인 경우에는 코팅 후 남게 되는 레지스트층이 너무 얇아 원하는 두께의 패턴을 형성하기 어렵고, 30중량%를 초과하면 코팅 균일성이 저 하될 우려가 있다. The photoresist composition according to the present invention includes a photoresist polymer including a repeating unit represented by Formula 2, a photoacid generator for generating an acid and an organic solvent, and may further include various additives as necessary. . The content of the photoresist polymer including the repeating unit represented by Formula 2 is preferably 1 to 30% by weight based on the total photoresist composition. If the content of the photoresist polymer is less than 1% by weight, the resist layer remaining after coating is too thin to form a pattern having a desired thickness, and if it exceeds 30% by weight, coating uniformity may be reduced.
상기 광산발생제는 노광에 의해 H+ 등 산성분을 생성하여, 상기 포토레지스트용 폴리머의 보호기를 탈보호시키는 역할을 하는 것으로서, 빛에 의해 산을 발생시킬 수 있는 화합물이면 무엇이든 사용할 수 있으며, 바람직하게는 유기술폰산 등의 황화염계 화합물, 오니움염 등의 오니움염계 화합물 및 이들의 혼합물을 사용할 수 있다. 광산발생제의 비한정적인 예로서는 157nm 및 193nm에서 흡광도가 적은 프탈이미도트리플루오로메탄술포네이트 (phthalimidotrifluoromethane sulfonate), 디니트로벤질토실레이트 (dinitrobenzyltosylate), n-데실디술폰(n-decyl disulfone), 나프틸이미도트리플루오로메탄술포네이트 (naphthylimido trifluoromethane sulfonate), 디페닐요도염 헥사플루오로포스페이트, 디페닐요도염 헥사플루오로 아르세네이트, 디페닐요도염 헥사플루오로 안티모네이트, 디페닐파라메톡시페닐설포늄 트리플레이트, 디페닐파라톨루에닐설포늄 트리플레이트, 디페닐파라이소부틸페닐설포늄 트리플레이트, 트리페닐설포늄 헥사플루오로 아르세네이트, 트리페닐설포늄 헥사플루오로 안티모네이트, 트리페닐설포늄 트리플레이트, 디부틸나프틸설포늄 트리플레이트 및 이들의 혼합물을 예시할 수 있다. 상기 광산발생제의 함량은 상기 포토레지스트용 폴리머에 대해 0.1 내지 20중량%인 것(즉, 폴리머 100중량부에 대하여 0.1 내지 20중량부)이 바람직하다. 만약 0.1 중량% 미만인 경우에는 포토레지스트 조성물의 빛에 대한 민감도가 저하되어 보호기의 탈보호가 곤란할 염려가 있고, 20중량%를 초과하면 광산발생제에서 다량의 산이 발생하 여 레지스트 패턴의 단면이 불량해질 염려가 있다. The photoacid generator generates an acid component such as H + by exposure, and serves to deprotect the protecting group of the photoresist polymer, and any compound capable of generating an acid by light may be used. Preferably, sulfide salt compounds such as eutectic acid and the like, and onium salt compounds such as onium salt and mixtures thereof can be used. Non-limiting examples of photoacid generators include phthalimidotrifluoromethane sulfonate, dinitrobenzyltosylate, n-decyl disulfone, nap having low absorbance at 157 nm and 193 nm. Naphthylimido trifluoromethane sulfonate, diphenylurodoxyl hexafluorophosphate, diphenylurodoxyl hexafluoro arsenate, diphenylurodoxyl hexafluoro antimonate, diphenylparamethoxyphenylsulfonium Triflate, Diphenylparatoluenylsulfonium Triflate, Diphenylparaisobutylphenylsulfonium Triflate, Triphenylsulfonium Hexafluoro Arsenate, Triphenylsulfonium Hexafluoro Antimonate, Triphenylsulfonium Triflate, dibutylnaphthylsulfonium triflate, and mixtures thereof. The content of the photoacid generator is preferably 0.1 to 20% by weight based on the photoresist polymer (that is, 0.1 to 20 parts by weight based on 100 parts by weight of the polymer). If it is less than 0.1 wt%, the sensitivity of the photoresist composition to light may be deteriorated, which may make it difficult to deprotect the protecting group. If it exceeds 20 wt%, a large amount of acid may be generated in the photoacid generator, resulting in poor cross-section of the resist pattern. There is concern.
본 발명에 따른 포토레지스트 조성물의 나머지 성분을 구성하는 유기용매로는 포토레지스트 조성물의 제조에 통상적으로 사용되는 다양한 유기 용매를 광범위하게 사용할 수 있으며, 비한정적인 예로는 에틸렌글리콜모노메틸에틸, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노아세테이트, 디에틸렌글리콜, 디에틸렌글리콜모노에틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜, 프로필렌글리콜모노아세테이트, 톨루엔, 자일렌, 메틸에틸케톤, 메틸이소아밀케톤, 사이클로헥산온, 디옥산, 메틸락테이트, 에틸락테이트, 메틸피루베이트, 에틸피루베이트, 메틸메톡시프로피오네이트, 에틸에톡시 프로피오네이트, N,N-디메틸포름아마이드, N,N-디메틸아세트아마이드, N-메틸 2-피롤리돈, 3-에톡시에틸프로피오네이트, 2-헵탄온, 감마-부티로락톤, 2-히드록시프로피온산에틸, 2-히드록시 2-메틸프로피온산에틸, 에톡시초산에틸, 히드록시초산에틸, 2-히드록시 3-메틸부탄산메틸, 3-메톡시 2-메칠프로피온산메틸, 3-에톡시프로피온산에틸, 3-메톡시 2-메틸프로피온산에틸, 초산에틸, 초산부틸 및 이들의 혼합물을 예시할 수 있다.As the organic solvent constituting the remaining components of the photoresist composition according to the present invention can be used a wide variety of organic solvents commonly used in the preparation of the photoresist composition, non-limiting examples include ethylene glycol monomethyl ethyl, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol, propylene glycol monoacetate, toluene, xylene, methyl ethyl ketone, Methyl isoamyl ketone, cyclohexanone, dioxane, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxy propionate, ethyl ethoxy propionate, N, N-dimethylformamide , N, N-dimethylacetamide, N-methyl 2-pyrrolidone, 3-ethoxyethyl Propionate, 2-heptanone, gamma-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy 2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxy acetate, 2-hydroxy 3-methyl moiety Methyl carbonate, methyl 3-methoxy 2-methylpropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxy 2-methylpropionate, ethyl acetate, butyl acetate and mixtures thereof.
또한, 본 발명에 따른 포토레지스트 조성물은 필요에 따라 유기염기를 더욱 포함할 수 있으며, 상기 유기염기의 비한정적인 예로는 트리에틸아민, 트리이소부틸아민, 트리이소옥틸아민, 디에탄올아민, 트리에탄올아민 및 이들의 혼합물을 예 시할 수 있다. 상기 유기염기의 함량은 전체 포토레지스트 조성물에 대하여 0.01 내지 10중량%인 것이 바람직하다. 유기염기의 함량이 0.01중량% 미만이면 레지스트 패턴에 티탑(t-top) 현상이 발생할 염려가 있고, 함량이 10중량%를 초과하면 포토레지스트 조성물의 감도가 떨어져 패턴 형성율이 저하될 염려가 있다. In addition, the photoresist composition according to the present invention may further include an organic base as needed, non-limiting examples of the organic base is triethylamine, triisobutylamine, triisooctylamine, diethanolamine, triethanol Amine and mixtures thereof can be exemplified. The content of the organic base is preferably 0.01 to 10% by weight based on the total photoresist composition. If the content of the organic base is less than 0.01% by weight, a t-top phenomenon may occur in the resist pattern, and if the content is more than 10% by weight, the sensitivity of the photoresist composition may be reduced and the pattern formation rate may be lowered. .
본 발명에 따른 포토레지스트 조성물은 상기 포토레지스트용 폴리머, 광산발생제, 유기용매 및 필요에 따라 각종 첨가제를 배합하고, 필요에 따라 필터로 여과하여 제조할 수 있으며, 이때, 전체 포토레지스트 조성물에 대하여 고형분 농도가 내지 1 내지 30중량%가 되도록 하는 것이 바람직하다. 상기 고형분의 농도가 1중량% 미만인 경우에는 레지스트층이 너무 얇아 원하는 두께의 패턴을 형성하기 어렵고, 30중량%를 초과하면 코팅층 균일성이 저하될 우려가 있다.The photoresist composition according to the present invention may be prepared by blending the photoresist polymer, a photoacid generator, an organic solvent, and various additives as necessary, and filtering by a filter as necessary, wherein the whole photoresist composition It is preferable to make solid content concentration into 1 to 30 weight%. When the concentration of the solid content is less than 1% by weight, the resist layer is too thin to form a pattern having a desired thickness, and when it exceeds 30% by weight, the coating layer uniformity may be deteriorated.
본 발명에 따른 포토레지스트 조성물을 이용하여, 포토레지스트 패턴을 형성하기 위해서는, 먼저, 실리콘 웨이퍼, 알루미늄 기판 등의 기판에 스핀 코터 등을 이용하여 상기 포토레지스트 조성물을 도포하여 포토레지스트막을 형성하고, 상기 포토레지스트막을 소정 패턴으로 노광 및 현상하는 통상의 포토리소그라피 공정을 사용할 수 있으며, 형성된 포토레지스트 패턴을 이용하여, 원하는 회로패턴을 갖는 반도체 소자를 제조할 수 있다. 상기 현상 공정에 사용되는 현상액으로는 수산화나트륨, 수산화칼륨, 탄산나트륨, 테트라메틸암모늄 히드록사이드(TMAH) 등의 알칼리성 화합물을 0.1 내지 10중량% 농도의 알칼리 수용액을 사용할 수 있으며, 필요에 따라 상기 현상액에 메탄올, 에탄올 등과 같은 수용성 유기용매 및 계면활성제를 적정량 첨가하여 사용할 수도 있다. 또한 이와 같은 현상 공정을 수행한 후에는 초순수로 기판을 세정하는 세정 공정을 더욱 수행할 수도 있다.In order to form a photoresist pattern using the photoresist composition according to the present invention, first, the photoresist composition is applied to a substrate such as a silicon wafer or an aluminum substrate using a spin coater to form a photoresist film. A conventional photolithography process of exposing and developing the photoresist film in a predetermined pattern can be used, and a semiconductor device having a desired circuit pattern can be manufactured using the formed photoresist pattern. As a developer used in the developing step, an alkaline aqueous solution of 0.1 to 10% by weight of an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide (TMAH), and the like can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added to the mixture. In addition, after the development process, the cleaning process may be further performed to clean the substrate with ultrapure water.
이하, 구체적인 실시예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기 실시예에 의하여 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples.
[실시예 1] 상기 화학식 1로 표시되는 모노머 제조 Example 1 Preparation of Monomers Represented by
1) 디사이클로펜타디엔의 분해(cracking) 1) Cracking Dicyclopentadiene
디사이클로펜타디엔(dicyclopentadiene) 450g을 220℃로 가열/교반하는 파라핀 오일(Paraffin oil)에 떨어뜨리고, 발생하는 증기를 40~45℃로 냉각시킨 후, 이를 10℃ 이하의 플라스크(flask)에서 회수하여, 사이클로펜타디엔(cyclopentadiene) 390g을 얻었다.450 g of dicyclopentadiene was dropped in paraffin oil heated / stirred to 220 ° C., the resulting vapor was cooled to 40-45 ° C., and then recovered in a flask of 10 ° C. or less. Thus, 390 g of cyclopentadiene were obtained.
2) 반응식 1의 화합물 (A) 제조 2) Preparation of Compound (A) of
2,5-디히드로-피롤 1당량 및 벤젠 1.3kg을 플라스크에 넣고, 이를 교반하면서 사이클로펜타디엔 190g을 적가하였다. 상기 과정은 적가시 온도 증가로 기체가 발생되는 것을 방지하기 위하여, 드라이 아이스 배스(bath)에서 수행되었다. 적가가 완결된 후, 실온까지 온도가 서서히 오르도록 방치하고, 1일간 더 교반하여 반 응식 1의 화합물 (A) 304g(수율:80%)을 제조하였다{H-NMR(CDCl3, 내부표준물질):δ(ppm), 1.60(CH, 2H), 1.82(CH2, 2H), 2.0(NH, 1H), 2.26(CH, 1H), 2.71(CH2, 4H), 5.60(CH, 2H)}.One equivalent of 2,5-dihydro-pyrrole and 1.3 kg of benzene were placed in a flask, and 190 g of cyclopentadiene was added dropwise with stirring. The procedure was carried out in a dry ice bath to prevent the evolution of gas with temperature increase during dropping. After completion of the dropwise addition, the temperature was gradually raised to room temperature and stirred for 1 day to prepare 304 g of Compound (A) of Reaction 1 (yield: 80%) {H-NMR (CDCl 3 , internal standard) ): δ (ppm), 1.60 (CH, 2H), 1.82 (CH 2 , 2H), 2.0 (NH, 1H), 2.26 (CH, 1H), 2.71 (CH 2 , 4H), 5.60 (CH, 2H) }.
3) 반응식 1의 화합물 (B) 제조 3) Preparation of Compound (B) of
상기 반응식 1의 화합물 (A) 0.5mol(67.61g) 및 탄산나트륨(sodium carbonate, Na2CO3) 1.0mol(106g)을 메틸렌 클로라이드 700ml에 녹인 혼합액에, 과초산(peracetic acid) 72g(0.4mol)에 아세트산나트륨(sodium acetate) 2g을 용해시킨 혼합액을 적가한 후, 20℃에서 30~45분간 교반하고, 상온에서 1시간동안 더욱 교반시켰다. 교반이 완결된 후, 반응물을 감압 증류하여, 고체를 걸러내고, 메틸렌 클로라이드로 3회 세척하여, 에폭시드를 갖는 노보넨 디히드로피롤 화합물(반응식 1의 화합물 (B)) 55.4g(수율%:82)을 제조하였다{H-NMR(CDCl3, 내부표준물질):δ(ppm), 1.43(CH2, 2H), 1.65(CH, 2H), 1.75(CH. 2H), 2.0(NH, 1H), 2.71(CH2, 4H), 2.86(CH, 2H)}. 0.5 g (67.61 g) of Compound (A) and 1.0 mol (106 g) of sodium carbonate (Na 2 CO 3 ) were dissolved in 700 ml of methylene chloride, and 72 g (0.4 mol) of peracetic acid. After dropwise adding a mixed solution of 2 g of sodium acetate, the mixture was stirred at 20 ° C. for 30 to 45 minutes, and further stirred at room temperature for 1 hour. After stirring was complete, the reaction was distilled under reduced pressure, the solid was filtered off, washed three times with methylene chloride, and 55.4 g of a norbornene dihydropyrrole compound (compound (B) of Scheme 1) having an epoxide (yield: 82) was prepared {H-NMR (CDCl 3 , internal standard): δ (ppm), 1.43 (CH 2 , 2H), 1.65 (CH, 2H), 1.75 (CH. 2H), 2.0 (NH, 1H ), 2.71 (CH 2 , 4H), 2.86 (CH, 2H)}.
4) 화학식 1로 표시되는 모노머 제조 4) Preparation of monomer represented by formula (1 )
상기 에폭시드를 갖는 노보넨 디히드로피롤 화합물 50g을 냉증류수 500ml에 넣고, 1시간 동안 빠르게 교반시켜, 반응식 1의 화합물 (C)를 제조하고, 상기 반응 식 1의 화합물 (C) 0.28mol(47.38g) 및 트리에틸아민 0.32mol(44.48ml)을 THF 250ml에 용해시킨 혼합액에 메타 아크릴로일 클로라이드 0.32mol(26ml)를 적하 깔대기를 이용하여, 천천히 첨가한 후, 2시간 동안 실온에서 반응시켰다. 반응이 완결된 후, 회전진공농축기(rotary evaporator)로 과량의 THF를 제거하고, 잔존하는 반응물을 물 500ml에 첨가하였다. 다음으로, 물이 첨가된 반응물을 묽은 염산으로 중화시키고, 디에틸 에테르로 추출한 후, 무수 마그네슘 설페이트로 건조시킨 후, 컬럼 크로마토그래피(Rf=0.2)로 정제하여 화학식 1로 표시되는 모노머를 72% 수율로 제조하였다{H-NMR(CDCl3, 내부표준물질):δ(ppm), 1.43(CH2, 2H), 1.51(CH, 1H), 1.65(CH, 2H), 1.93(CH3, 3H), 2.0(NH, OH, 2H), 2.02(CH, 1H), 2.71(CH2, 4H), 3.75(CH, 1H), 3.98(CH, 1H), 5.58(H,1H), 6.15(H,1H)}.50 g of the norbornene dihydropyrrole compound having the epoxide was added to 500 ml of cold distilled water, and rapidly stirred for 1 hour to prepare Compound (C) of
[실시예 2-1] 상기 화학식 5a로 표시되는 폴리머의 제조 Example 2-1 Preparation of Polymer Represented by Chemical Formula 5a
2-메틸-2-아다멘틸 메타아크릴레이트 18.75g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 13.71g(0.058mol), 상기 화학식 1로 표시되는 모노머 0.47g(0.002mol), 및 아조비스(이소부티로니트릴)(AIBN) 10g을 무수 THF 150g에 용해시키고, 동결방법으로 앰플(ampoule)을 사용하여 가스를 제거한 후, 반응물을 66℃에서 12시간 동안 중합 반응시켰으며, 중합된 반응물을 과량의 디에틸에테르에 천천히 떨어뜨려 침전시키고, 다시 THF에 용해시킨 후, 디에틸 에테르에서 재침전시켜, 상기 화학식 5a로 표 시되는 포토레지스트용 폴리머를 제조하였다. 18.75 g (0.080 mol) of 2-methyl-2-adamantyl methacrylate, 10.21 g (0.060 mol) of gamma butyrolactone methacrylate, 13.71 g (0.058 mol) of hydroxy adamantyl methacrylate, the
[실시예 2-2] 상기 화학식 5a로 표시되는 폴리머의 제조 Example 2-2 Preparation of the Polymer Represented by Chemical Formula 5a
2-메틸-2-아다멘틸 메타아크릴레이트 18.75g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 12.76g(0.054mol), 상기 화학식 1로 표시되는 모노머 1.42g(0.006mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5a로 표시되는 포토레지스트용 폴리머를 제조하였다. 18.75 g (0.080 mol) of 2-methyl-2-adamantyl methacrylate, 10.21 g (0.060 mol) of gamma butyrolactone methacrylate, 12.76 g (0.054 mol) of hydroxy adamantyl methacrylate, the formula 1 A polymer for photoresist represented by Chemical Formula 5a was prepared by the same method as Example 2-1, except that 1.42 g (0.006 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Prepared.
[실시예 2-3] 상기 화학식 5a로 표시되는 폴리머의 제조 Example 2-3 Preparation of Polymer Represented by Formula 5a
2-메틸-2-아다멘틸 메타아크릴레이트 18.75g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 11.82g(0.050mol), 상기 화학식 1로 표시되는 모노머 2.37g(0.010mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5a로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-methyl-2-adamantyl methacrylate 18.75 g (0.080 mol), gamma butyrolactone methacrylate 10.21 g (0.060 mol), hydroxy adamantyl methacrylate 11.82 g (0.050 mol), the formula 1 A photoresist polymer represented by Chemical Formula 5a was prepared in the same manner as in Example 2-1, except that 2.37 g (0.010 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Prepared.
[실시예 3-1] 상기 화학식 5b로 표시되는 폴리머의 제조 Example 3-1 Preparation of Polymer Represented by Chemical Formula 5b
2-에틸-2-아다멘틸 메타아크릴레이트 19.87g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 13.71g(0.058mol), 상기 화학식 1로 표시되는 모노머 0.47g(0.002mol) 및 아조비스 (이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5b로 표시되는 포토레지스트용 폴리머를 제조하였다. 19.87 g (0.080 mol) of 2-ethyl-2-adamantyl methacrylate, 10.21 g (0.060 mol) of gamma butyrolactone methacrylate, 13.71 g (0.058 mol) of hydroxy adamantyl methacrylate, the chemical formula 1 A photoresist polymer represented by Chemical Formula 5b was prepared in the same manner as in Example 2-1, except that 0.47 g (0.002 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Prepared.
[실시예 3-2] 상기 화학식 5b로 표시되는 폴리머의 제조 Example 3-2 Preparation of the Polymer Represented by Chemical Formula 5b
2-에틸-2-아다멘틸 메타아크릴레이트 19.87g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 12.76g(0.054mol), 상기 화학식 1로 표시되는 모노머 1.42g(0.006mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5b로 표시되는 포토레지스트용 폴리머를 제조하였다. 19.87 g (0.080 mol) of 2-ethyl-2-adamantyl methacrylate, 10.21 g (0.060 mol) of gamma butyrolactone methacrylate, 12.76 g (0.054 mol) of hydroxy adamantyl methacrylate, the chemical formula 1 A photoresist polymer represented by Chemical Formula 5b was prepared in the same manner as in Example 2-1, except that 1.42 g (0.006 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Prepared.
[실시예 3-3] 상기 화학식 5b로 표시되는 폴리머의 제조 Example 3-3 Preparation of the Polymer Represented by Chemical Formula 5b
2-에틸-2-아다멘틸 메타아크릴레이트 19.87g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 11.82g(0.050mol), 상기 화학식 1로 표시되는 모노머 2.37g(0.010mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5b로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-ethyl-2-adamantyl methacrylate 19.87 g (0.080 mol), gamma butyrolactone methacrylate 10.21 g (0.060 mol), hydroxy adamantyl methacrylate 11.82 g (0.050 mol), the formula 1 A photoresist polymer represented by Chemical Formula 5b was prepared in the same manner as in Example 2-1, except that 2.37 g (0.010 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Prepared.
[실시예 4-1] 상기 화학식 5c로 표시되는 폴리머의 제조 Example 4-1 Preparation of a Polymer Represented by Chemical Formula 5c
2-에틸-2-사이클로헥실 메타아크릴레이트 15.70g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 13.71g(0.058mol), 상기 화학식 1로 표시되는 모노머 0.47g(0.002mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5c로 표시되는 포토레지스트용 폴리머를 제조하였다. 15.70 g (0.080 mol) of 2-ethyl-2-cyclohexyl methacrylate, 10.21 g (0.060 mol) of gamma butyrolactone methacrylate, 13.71 g (0.058 mol) of hydroxy adamantyl methacrylate, the formula 1 A photoresist polymer represented by Chemical Formula 5c was prepared by the same method as Example 2-1, except that 0.47 g (0.002 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Prepared.
[실시예 4-2] 상기 화학식 5c로 표시되는 폴리머의 제조 Example 4-2 Preparation of the Polymer Represented by Chemical Formula 5c
2-에틸-2-사이클로헥실 메타아크릴레이트 15.70g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 12.76g(0.054mol), 상기 화학식 1로 표시되는 모노머 1.42g(0.006mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5c로 표시되는 포토레지스트용 폴리머를 제조하였다. 15.70 g (0.080 mol) of 2-ethyl-2-cyclohexyl methacrylate, 10.21 g (0.060 mol) of gamma butyrolactone methacrylate, 12.76 g (0.054 mol) of hydroxy adamantyl methacrylate, the formula 1 A photoresist polymer represented by Chemical Formula 5c was prepared by the same method as Example 2-1, except that 1.42 g (0.006 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Prepared.
[실시예 4-3] 상기 화학식 5c로 표시되는 폴리머의 제조 Example 4-3 Preparation of the Polymer Represented by Chemical Formula 5c
2-에틸-2-사이클로헥실 메타아크릴레이트 15.70g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 11.82g(0.050mol), 상기 화학식 1로 표시되는 모노머 2.37g(0.010mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5c로 표시되는 포토레지스트용 폴리머를 제조하였다. 15.70 g (0.080 mol) of 2-ethyl-2-cyclohexyl methacrylate, 10.21 g (0.060 mol) of gamma butyrolactone methacrylate, 11.82 g (0.050 mol) of hydroxy adamantyl methacrylate, the formula 1 A photoresist polymer represented by Chemical Formula 5c was prepared by the same method as Example 2-1, except that 2.37 g (0.010 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Prepared.
[실시예 5-1] 상기 화학식 5d로 표시되는 폴리머의 제조 Example 5-1 Preparation of the Polymer Represented by Chemical Formula 5d
2-에틸-2-사이클로펜틸 메타아크릴레이트 14.58g(0.080mol), 감마 부티로락 톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 13.71g(0.058mol), 상기 화학식 1로 표시되는 모노머 0.47g(0.002mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5d로 표시되는 포토레지스트용 폴리머를 제조하였다. 14.58 g (0.080 mol) of 2-ethyl-2-cyclopentyl methacrylate, 10.21 g (0.060 mol) of gamma butyrolactone methacrylate, 13.71 g (0.058 mol) of hydroxy adamantyl methacrylate, Formula 1 A photoresist polymer represented by Chemical Formula 5d in the same manner as in Example 2-1, except that 0.47 g (0.002 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Was prepared.
[실시예 5-2] 상기 화학식 5d로 표시되는 폴리머의 제조 Example 5-2 Preparation of the Polymer Represented by Chemical Formula 5d
2-에틸-2-사이클로펜틸 메타아크릴레이트 14.58g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 12.76g(0.054mol), 상기 화학식 1로 표시되는 모노머 1.42g(0.006mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5d로 표시되는 포토레지스트용 폴리머를 제조하였다. 14.58 g (0.080 mol) of 2-ethyl-2-cyclopentyl methacrylate, 10.21 g (0.060 mol) of gamma butyrolactone methacrylate, 12.76 g (0.054 mol) of hydroxy adamantyl methacrylate, to Chemical Formula 1 A photoresist polymer represented by Chemical Formula 5d was prepared in the same manner as in Example 2-1, except that 1.42 g (0.006 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Prepared.
[실시예 5-3] 상기 화학식 5d로 표시되는 폴리머의 제조 Example 5-3 Preparation of the Polymer Represented by Chemical Formula 5d
2-에틸-2-사이클로펜틸 메타아크릴레이트 14.58g(0.080mol), 감마 부티로락톤 메타아크릴레이트 10.21g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 11.82g(0.050mol), 상기 화학식 1로 표시되는 모노머 2.37g(0.010mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5d로 표시되는 포토레지스트용 폴리머를 제조하였다. 14.58 g (0.080 mol) of 2-ethyl-2-cyclopentyl methacrylate, 10.21 g (0.060 mol) of gamma butyrolactone methacrylate, 11.82 g (0.050 mol) of hydroxy adamantyl methacrylate, as
[실시예 6-1] 상기 화학식 5e로 표시되는 폴리머의 제조 Example 6-1 Preparation of a Polymer Represented by Chemical Formula 5e
2-메틸-2-아다멘틸 메타아크릴레이트 18.75g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 13.71g(0.058mol), 상기 화학식 1로 표시되는 모노머 0.47g(0.002mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5e로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-methyl-2-adamantyl methacrylate 18.75 g (0.080 mol), norbornene lactone methacrylate 13.33 g (0.060 mol), hydroxy adamantyl methacrylate 13.71 g (0.058 mol), represented by the formula (1) A photoresist polymer represented by Chemical Formula 5e was prepared by the same method as Example 2-1, except that 0.47 g (0.002 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
[실시예 6-2] 상기 화학식 5e로 표시되는 폴리머의 제조 Example 6-2 Preparation of the Polymer Represented by Chemical Formula 5e
2-메틸-2-아다멘틸 메타아크릴레이트 18.75g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 12.76g(0.054mol), 상기 화학식 1로 표시되는 모노머 1.42g(0.006mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5e로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-methyl-2-adamantyl methacrylate 18.75 g (0.080 mol), norbornene lactone methacrylate 13.33 g (0.060 mol), hydroxy adamantyl methacrylate 12.76 g (0.054 mol), represented by the formula (1) A photoresist polymer represented by Chemical Formula 5e was prepared by the same method as Example 2-1, except that 1.42 g (0.006 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
[실시예 6-3] 상기 화학식 5e로 표시되는 폴리머의 제조 Example 6-3 Preparation of the Polymer Represented by Chemical Formula 5e
2-메틸-2-아다멘틸 메타아크릴레이트 18.75g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 11.82g(0.050mol), 상기 화학식 1로 표시되는 모노머 2.37g(0.010mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5e로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-methyl-2-adamantyl methacrylate 18.75 g (0.080 mol), norbornene lactone methacrylate 13.33 g (0.060 mol), hydroxy adamantyl methacrylate 11.82 g (0.050 mol), represented by the formula (1) A photoresist polymer represented by Chemical Formula 5e was prepared by the same method as Example 2-1, except that 2.37 g (0.010 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
[실시예 7-1] 상기 화학식 5f로 표시되는 폴리머의 제조 Example 7-1 Preparation of Polymers Represented by Formula 5f
2-에틸-2-아다멘틸 메타아크릴레이트 19.87g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 13.71g(0.058mol), 상기 화학식 1로 표시되는 모노머 0.47g(0.002mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5f로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-ethyl-2-adamantyl methacrylate 19.87 g (0.080 mol), norbornene lactone methacrylate 13.33 g (0.060 mol), hydroxy adamantyl methacrylate 13.71 g (0.058 mol), represented by the formula A photoresist polymer represented by Chemical Formula 5f was prepared by the same method as Example 2-1, except that 0.47 g (0.002 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
[실시예 7-2] 상기 화학식 5f로 표시되는 폴리머의 제조 Example 7-2 Preparation of the Polymer Represented by Chemical Formula 5f
2-에틸-2-아다멘틸 메타아크릴레이트 19.87g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 12.76g(0.054mol), 상기 화학식 1로 표시되는 모노머 1.42g(0.006mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5f로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-ethyl-2-adamantyl methacrylate 19.87 g (0.080 mol), norbornene lactone methacrylate 13.33 g (0.060 mol), hydroxy adamantyl methacrylate 12.76 g (0.054 mol), represented by the formula (1) A photoresist polymer represented by Chemical Formula 5f was prepared by the same method as Example 2-1, except that 1.42 g (0.006 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
[실시예 7-3] 상기 화학식 5f로 표시되는 폴리머의 제조 Example 7-3 Preparation of the Polymer Represented by Chemical Formula 5f
2-에틸-2-아다멘틸 메타아크릴레이트 19.87g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 11.82g(0.050mol), 상기 화학식 1로 표시되는 모노머 2.37g(0.010mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5f로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-ethyl-2-adamantyl methacrylate 19.87 g (0.080 mol), norbornene lactone methacrylate 13.33 g (0.060 mol), hydroxy adamantyl methacrylate 11.82 g (0.050 mol), represented by the formula (1) A photoresist polymer represented by Chemical Formula 5f was prepared by the same method as Example 2-1, except that 2.37 g (0.010 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
[실시예 8-1] 상기 화학식 5g로 표시되는 폴리머의 제조 Example 8-1 Preparation of the Polymer Represented by Chemical Formula 5g
2-에틸-2-사이클로헥실 메타아크릴레이트 15.70g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 13.71g(0.058mol), 상기 화학식 1로 표시되는 모노머 0.47g(0.002mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5g로 표시되는 포토레지스트용 폴리머를 제조하였다. 15.70 g (0.080 mol) of 2-ethyl-2-cyclohexyl methacrylate, 13.33 g (0.060 mol) of norbornene lactone methacrylate, 13.71 g (0.058 mol) of hydroxy adamantyl methacrylate, represented by Chemical Formula 1 A photoresist polymer represented by Chemical Formula 5g was prepared by the same method as Example 2-1, except that 0.47 g (0.002 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
[실시예 8-2] 상기 화학식 5g로 표시되는 폴리머의 제조 Example 8-2 Preparation of the Polymer Represented by Chemical Formula 5g
2-에틸-2-사이클로헥실 메타아크릴레이트 15.70g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 12.76g(0.054mol), 상기 화학식 1로 표시되는 모노머 1.42g(0.006mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5g로 표시되는 포토레지스트용 폴리머를 제조하였다. 15.70 g (0.080 mol) of 2-ethyl-2-cyclohexyl methacrylate, 13.33 g (0.060 mol) of norbornene lactone methacrylate, 12.76 g (0.054 mol) of hydroxy adamantyl methacrylate, represented by Chemical Formula 1 A photoresist polymer represented by Chemical Formula 5g was prepared by the same method as Example 2-1, except that 1.42 g (0.006 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
[실시예 8-3] 상기 화학식 5g로 표시되는 폴리머의 제조 Example 8-3 Preparation of the Polymer Represented by Chemical Formula 5g
2-에틸-2-사이클로헥실 메타아크릴레이트 15.70g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 11.82g(0.050mol), 상기 화학식 1로 표시되는 모노머 2.37g(0.010mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일 한 방법으로 상기 화학식 5g로 표시되는 포토레지스트용 폴리머를 제조하였다. 15.70 g (0.080 mol) of 2-ethyl-2-cyclohexyl methacrylate, 13.33 g (0.060 mol) of norbornene lactone methacrylate, 11.82 g (0.050 mol) of hydroxy adamantyl methacrylate, represented by Chemical Formula 1 A photoresist polymer represented by Chemical Formula 5g was prepared by the same method as Example 2-1, except that 2.37 g (0.010 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. Prepared.
[실시예 9-1] 상기 화학식 5h로 표시되는 폴리머의 제조 Example 9-1 Preparation of the Polymer Represented by Chemical Formula 5h
2-에틸-2-사이클로펜틸 메타아크릴레이트 14.58g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 13.71g(0.058mol), 상기 화학식 1로 표시되는 모노머 0.47g(0.002mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5h로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-ethyl-2-cyclopentyl methacrylate 14.58 g (0.080 mol), norbornene lactone methacrylate 13.33 g (0.060 mol), hydroxy adamantyl methacrylate 13.71 g (0.058 mol), represented by the formula (1) A photoresist polymer represented by Chemical Formula 5h was prepared by the same method as Example 2-1, except that 0.47 g (0.002 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
[실시예 9-2] 상기 화학식 5h로 표시되는 폴리머의 제조 Example 9-2 Preparation of the Polymer Represented by Chemical Formula 5h
2-에틸-2-사이클로펜틸 메타아크릴레이트 14.58g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 12.76g(0.054mol), 상기 화학식 1로 표시되는 모노머 1.42g(0.006mol) 및 아조비스(이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5h로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-ethyl-2-cyclopentyl methacrylate 14.58 g (0.080 mol), norbornene lactone methacrylate 13.33 g (0.060 mol), hydroxy adamantyl methacrylate 12.76 g (0.054 mol), represented by the formula (1) A photoresist polymer represented by Chemical Formula 5h was prepared by the same method as Example 2-1, except that 1.42 g (0.006 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
[실시예 9-3] 상기 화학식 5h로 표시되는 폴리머의 제조 Example 9-3 Preparation of the Polymer Represented by Chemical Formula 5h
2-에틸-2-사이클로펜틸 메타아크릴레이트 14.58g(0.080mol), 노보넨락톤 메타아크릴레이트 13.33g(0.060mol), 히드록시 아다멘틸 메타아크릴레이트 11.82g(0.050mol), 상기 화학식 1로 표시되는 모노머 2.37g(0.010mol) 및 아조비스 (이소부티로니트릴)(AIBN) 10g을 사용한 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 상기 화학식 5h로 표시되는 포토레지스트용 폴리머를 제조하였다. 2-ethyl-2-cyclopentyl methacrylate 14.58 g (0.080 mol), norbornene lactone methacrylate 13.33 g (0.060 mol), hydroxy adamantyl methacrylate 11.82 g (0.050 mol), represented by the formula (1) A photoresist polymer represented by Chemical Formula 5h was prepared by the same method as Example 2-1, except that 2.37 g (0.010 mol) of monomer and 10 g of azobis (isobutyronitrile) (AIBN) were used. It was.
상기 실시예 2-1 내지 9-3에서 제조된 포토레지스트용 폴리머 사슬을 구성하는 반복단위의 몰비%, 중량평균분자량(Mw), 수평균분자량(Mn), 다분산도(pd) 및 수율(%)을 하기 표 1에 나타내었다. Molar ratio%, weight average molecular weight (Mw), number average molecular weight (Mn), polydispersity (pd), and yield (%) of the repeating units constituting the polymer chain for photoresist prepared in Examples 2-1 to 9-3 ( %) Is shown in Table 1 below.
상기 표 1로부터, 실시예 2-1 내지 9-3에서 제조된 포토레지스트용 폴리머는 노보넨 디히드로피롤계 모노머(d)를 약 1~5% 정도 함유하고 있음을 알 수 있다.From Table 1, it can be seen that the photoresist polymers prepared in Examples 2-1 to 9-3 contain about 1-5% of norbornene dihydropyrrole monomer (d).
[실시예 10-1 내지 10-24] 상기 실시예 2-1 내지 9-3에서 제조한 폴리머를 포함하는 포토레지스트 조성물 제조 [Examples 10-1 to 10-24] Preparation of a photoresist composition comprising the polymers prepared in Examples 2-1 to 9-3
상기 실시예 2-1에서 제조한 폴리머 2g 및 트리페닐설포늄 트리플레이트(TPS-105) 0.02g을 프로필렌글리콜모노메틸에테르아세테이트(PGMEA) 17g에 녹인 후, 0.20㎛ 필터로 여과시켜 포토레지스트 조성물을 제조하였고, 상기 실시예 2-1에서 제조한 포토레지스트용 고분자 2g 대신에, 실시예 2-2 내지 9-3에서 제조한 포토레지스트용 고분자 2g을 사용한 것을 제외하고는 이와 동일한 방법으로 포토레지스트 조성물을 제조하였다.2 g of the polymer prepared in Example 2-1 and 0.02 g of triphenylsulfonium triflate (TPS-105) were dissolved in 17 g of propylene glycol monomethyl ether acetate (PGMEA), and then filtered through a 0.20 µm filter to obtain a photoresist composition. The photoresist composition was prepared in the same manner except for using the photoresist polymer 2g prepared in Examples 2-2 to 9-3, instead of the photoresist polymer 2g prepared in Example 2-1. Was prepared.
[비교예 1] 화학식 6으로 표시되는 폴리머를 포함하는 포토레지스트 조성물 제조 Comparative Example 1 Preparation of a photoresist composition comprising a polymer represented by the formula (6)
하기 화학식 6으로 표시되는 폴리머 {HPLC conversion분석(mol ratio %) = 2-메틸-2-아다멘틸-메타아크릴레이트 : 감마 부틸로 락톤 메타아크릴레이트= 42.8 : 57.2, GPC 분석: Mn=4985, Mw=9578, PD=1.92, 저분자잔량=0.1%} 2g 및 트리페닐설포늄 트리플레이트 0.02g을 프로필렌글리콜모노메틸에테르아세테이트(PGMEA) 17g에 녹인 후, 0.20㎛ 필터로 여과시켜 포토레지스트 조성물을 제조하였다.The polymer represented by the following Chemical Formula 6 {HPLC conversion analysis (mol ratio%) = 2-methyl-2-adamantyl-methacrylate: gamma butyrolactone methacrylate = 42.8: 57.2, GPC analysis: Mn = 4985, Mw 295 and 0.02 g of triphenylsulfonium triflate were dissolved in 17 g of propylene glycol monomethyl ether acetate (PGMEA), and then filtered through a 0.20 μm filter to prepare a photoresist composition. .
[실시예 11-1 내지 11-24 및 비교예 2] 포토레지스트 조성물을 사용한 노광 패턴형성 및 PEB 온도변화에 따른 선폭변화 비교 [Examples 11-1 to 11-24 and Comparative Example 2] Comparison of line width change according to exposure pattern formation and PEB temperature change using photoresist composition
상기 실시예 10-1 내지 10-24 및 비교예 1에서 제조한 포토레지스트 조성물을 유기 저반사 방지 코팅조성물(BARC, DHA-A25)이 코팅된 실리콘 웨이퍼상에 두께가 0.20㎛ 되도록 스핀 코팅하여 포토레지스트 박막을 제조한 후, 120℃의 오븐에서 90초 동안 프리베이킹하고, 개구수 0.60인 ArF 엑시머 레이저 노광장비로 노광한 후, 120±3℃에서 90초 동안 다시 가열(PEB)하였다. 가열된 웨이퍼를 2.38 중량% 테트라메틸암모늄 하이드록사이드(TMAH) 수용액에 30초 동안 침지하여 현상함으로서, 0.1㎛의 동일라인(equal line) 및 스페이스 패턴의 PEB 온도변화에 따른 선폭변화 크기를 조사하였으며, 산확산 억제작용에 대한 에너지의 변화량 및 그 결과를 도 1 및 도 2에 나타내었다. The photoresist composition prepared in Examples 10-1 to 10-24 and Comparative Example 1 was spin coated on a silicon wafer coated with an organic anti-reflective coating composition (BARC, DHA-A25) so as to have a thickness of 0.20 μm. After the resist thin film was prepared, it was prebaked for 90 seconds in an oven at 120 ° C., exposed with an ArF excimer laser exposure apparatus having a numerical aperture of 0.60, and then heated again (PEB) at 120 ± 3 ° C. for 90 seconds. The heated wafer was developed by immersing in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to investigate the magnitude of the line width change according to the PEB temperature change of the same line and space pattern of 0.1 μm. , And the change amount of energy for the acid diffusion inhibitory action and the results are shown in FIGS. 1 and 2.
도 1은 본 발명의 실시예에 따른 포토레지스트용 고분자의 최적노광량(EOP) 변화를 나타낸 그래프이고, 도 2는 본 발명의 실시예에 따른 포토레지스트용 고분자의 노광 후 가열(PEB) 온도에 따른 100nm 패턴의 선폭크기 변화를 나타낸 그래프이다. 도 1로부터, 노보넨 디히드로피롤계 모노머를 포함하는 실시예 2-1 내지 9-3에서 제조된 포토레지스트용 폴리머들은 노보넨 디히드로피롤계 모노머를 포함하지 않는 비교예 1의 폴리머에 비하여 최적노광량(EOP)이 높음을 알 수 있고, 이로부터 노보넨 디히드로피롤계 염기성 모노머가 노광후 발생된 산의 확산을 조절하고 있음을 알 수 있다. 또한 도 2로부터, 실시예 2-1 내지 9-3에서 제조된 포토레지스트용 폴리머들이 노광후 선폭변화의 크기를 감소시키고 있음을 알 수 있다.1 is a graph showing a change in the optimum exposure amount (EOP) of the photoresist polymer according to an embodiment of the present invention, Figure 2 is a post-exposure heating (PEB) temperature of the photoresist polymer according to an embodiment of the present invention It is a graph showing the change in the line width of the 100nm pattern. From FIG. 1, the polymers for photoresists prepared in Examples 2-1 to 9-3 containing norbornene dihydropyrrole monomers are more optimal than those of Comparative Example 1 containing no norbornene dihydropyrrole monomers. It can be seen that the exposure dose (EOP) is high, and from this, it is understood that the norbornene dihydropyrrole basic monomer controls the diffusion of acid generated after exposure. 2, it can be seen that the photoresist polymers prepared in Examples 2-1 to 9-3 are reducing the magnitude of the line width change after exposure.
이상 상술한 바와 같이, 본 발명에 따른 포토레지스트용 모노머, 폴리머 및 이를 포함하는 포토레지스트 조성물은 248nm 또는 193nm 이하의 단파장 노광원을 이용하는 포토리소그라피 공정에 있어서, 라인에지러프니스를 줄이고, 노광 후, 온도 증가에 따른 패턴의 선폭 변화를 감소시킬 뿐만 아니라, 고해상도, 높은 건식 식각 안정성 및 넓은 공정여유도를 갖는다.As described above, the photoresist monomer, the polymer and the photoresist composition including the same according to the present invention reduce the line edge roughness in the photolithography process using a short wavelength exposure source of 248 nm or 193 nm or less, and after exposure, In addition to reducing the line width variation of the pattern with increasing temperature, it has high resolution, high dry etching stability and wide process margin.
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| CN109438657A (en) * | 2018-11-01 | 2019-03-08 | 无锡阿科力科技股份有限公司 | A kind of polyurethane acroleic acid oligomer and its preparation method and application |
| WO2021134951A1 (en) * | 2019-12-31 | 2021-07-08 | 广东生益科技股份有限公司 | Thermosetting resin composition and prepreg, laminate and printed circuit board using same |
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| CN109438657A (en) * | 2018-11-01 | 2019-03-08 | 无锡阿科力科技股份有限公司 | A kind of polyurethane acroleic acid oligomer and its preparation method and application |
| WO2021134951A1 (en) * | 2019-12-31 | 2021-07-08 | 广东生益科技股份有限公司 | Thermosetting resin composition and prepreg, laminate and printed circuit board using same |
| US12122904B2 (en) | 2019-12-31 | 2024-10-22 | Shengyi Technology Co., Ltd. | Thermosetting resin composition and prepreg, laminate and printed circuit board using same |
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