KR20050066185A - Cleaning solution for photoresist and method for forming pattern using the same - Google Patents
Cleaning solution for photoresist and method for forming pattern using the same Download PDFInfo
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- KR20050066185A KR20050066185A KR1020030097436A KR20030097436A KR20050066185A KR 20050066185 A KR20050066185 A KR 20050066185A KR 1020030097436 A KR1020030097436 A KR 1020030097436A KR 20030097436 A KR20030097436 A KR 20030097436A KR 20050066185 A KR20050066185 A KR 20050066185A
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- photoresist
- cleaning liquid
- liquid composition
- pattern
- formula
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 51
- 238000004140 cleaning Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 3
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010884 ion-beam technique Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 abstract description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- -1 alcohol compound Chemical class 0.000 abstract 1
- 230000018109 developmental process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000007261 regionalization Effects 0.000 description 4
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic acids
-
- 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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Abstract
본 발명은 포토레지스트 패턴 형성시, 현상의 마지막 단계에서 반도체기판을 세정하는데 사용하는 포토레지스트 세정액 조성물 및 이를 이용한 패턴 형성방법에 관한 것으로, 본 발명의 세정액 조성물은 물을 주성분으로 하고, 첨가제로서 하기 화학식 1로 표시되는 N,N-디알킬(메트)아크릴아마이드계 계면활성제 및 알코올 화합물을 포함하는 것으로 종래에 세정액으로 사용하던 증류수보다 표면장력이 낮기 때문에 패턴 붕괴 현상을 개선시키고, 패턴 형성 공정의 안정화를 가져올 수 있다.The present invention relates to a photoresist cleaning liquid composition used to clean a semiconductor substrate in the final stage of development when forming a photoresist pattern, and a pattern forming method using the same. The cleaning liquid composition of the present invention contains water as a main component, It contains N, N-dialkyl (meth) acrylamide-based surfactant and alcohol compound represented by the formula (1) and has a lower surface tension than distilled water, which has been conventionally used as a cleaning liquid. It can lead to stabilization.
[화학식 1][Formula 1]
상기 식에서, Where
R1은 수소 또는 C1∼C5의 알킬이고,R 1 is hydrogen or C 1 -C 5 alkyl,
R2 및 R3은 C1∼C5의 알킬이며,R 2 and R 3 are C 1 -C 5 alkyl,
m은 1 내지 500 중에서 선택되는 정수이다.m is an integer selected from 1 to 500.
Description
본 발명은 포토레지스트 패턴 형성시, 현상의 마지막 단계에서 반도체기판을 세정하는데 사용하는 포토레지스트 세정액 조성물에 관한 것으로, 더욱 상세하게는 물을 주성분으로 하고, 첨가제로서 N,N-디알킬(메트)아크릴아마이드를 포함하는 포토레지스트 세정액 조성물 및 이를 이용한 패턴 형성방법에 관한 것이다.The present invention relates to a photoresist cleaning liquid composition used to clean a semiconductor substrate at the end of development in forming a photoresist pattern, and more particularly, based on water as a main component and N, N-dialkyl (meth) as an additive. It relates to a photoresist cleaning liquid composition containing acrylamide and a pattern forming method using the same.
근래에 디바이스가 점점 미세화 되어감에 따라 포토레지스트 패턴의 종횡비 (aspect ratio; 포토레지스트 두께, 즉 형성된 패턴의 높이/선폭)가 높아지게 되는데, 그 결과 세정 공정시에 패턴이 붕괴하는 문제가 발생한다. In recent years, as the device becomes more and more finer, the aspect ratio (photoresist thickness, ie, the height / line width of the formed pattern) of the photoresist pattern becomes high. As a result, the pattern collapses during the cleaning process.
포토레지스트 패턴의 붕괴는 형성된 패턴의 높이가 임계 높이를 넘는 경우, 모세관력 (capillary force)이 포토레지스트 자체의 탄성력을 능가하게 되어 나타난다. 이를 해결하기 위하여 포토레지스트 내부의 탄성을 증가시키거나 포토레지스트 자체의 표면장력을 낮춰 피식각층과 포토레지스트 사이의 부착력을 높이는 방법 등을 시도할 수 있다.The collapse of the photoresist pattern appears when the capillary force exceeds the elastic force of the photoresist itself when the height of the formed pattern exceeds the critical height. In order to solve this problem, a method of increasing the elasticity inside the photoresist or lowering the surface tension of the photoresist itself may increase the adhesion between the etched layer and the photoresist.
일반적으로, 반도체기판 상에 포토레지스트 패턴을 형성하는 방법은 먼저 반도체기판 상에 피식각층을 형성한 다음, 피식각층 위에 포토레지스트 막을 형성하고, 노광 및 현상 공정으로 상기 피식각층의 일부를 노출시켜 포토레지스트 패턴을 형성한다. 이때 포지티브형 포토레지스트 막을 사용한 경우에는 노광 영역의 포토레지스트 막이 현상액에 의해 제거되어 포토레지스트 패턴이 형성된다.In general, a method of forming a photoresist pattern on a semiconductor substrate may be performed by first forming an etched layer on the semiconductor substrate, then forming a photoresist layer on the etched layer, and exposing a portion of the etched layer by exposure and development. A resist pattern is formed. At this time, in the case of using a positive photoresist film, the photoresist film in the exposure area is removed by a developer to form a photoresist pattern.
그리고, 마지막 공정으로 반도체기판을 스핀시키면서 스핀 장치의 상부로부터 증류수를 분사시켜서, 잔류하는 포토레지스트 막을 제거하는 세정공정을 거치는데, 이 과정에서 증류수의 표면장력이 높아 패턴이 붕괴하는 문제점이 발생한다.In the final process, the semiconductor substrate is spun while the distilled water is sprayed from the top of the spin apparatus to remove the remaining photoresist film. In this process, the surface tension of the distilled water is high, resulting in a pattern collapse. .
종래의 경우, 미합중국 특허 제5,374,502호에서는 tert-아밀 알코올, 2-메틸-1-부탄올, 1-부탄올, tert-부틸 알코올, 3-펜탄올 및 이소부틸 알코올 등을 포함하는 세정액을 사용하여 높은 종횡비를 가지는 포토레지스트 패턴의 붕괴를 방지할 수 있다고 기재하고 있다.In the prior art, US Pat. No. 5,374,502 discloses a high aspect ratio using a cleaning liquid comprising tert-amyl alcohol, 2-methyl-1-butanol, 1-butanol, tert-butyl alcohol, 3-pentanol, isobutyl alcohol, and the like. It is described that the collapse of the photoresist pattern having can be prevented.
또한, 미합중국 특허 제5,474,877호에서는 열을 가하여 표면장력을 낮춘 세정액을 세정공정에 사용함으로써 포토레지스트 패턴의 붕괴를 방지할 수 있다고 기재하고 있다. In addition, US Pat. No. 5,474,877 discloses that a cleaning liquid having a low surface tension by applying heat can be used in the cleaning process to prevent the collapse of the photoresist pattern.
또한, 현상액에 계면활성제를 첨가하여 패턴의 붕괴를 방지하는 방법도 있으나, 이는 세정액에 계면활성제를 첨가하는 경우보다는 그 효과가 낮으며, 경우에 따라 패턴의 크기를 불균일하게 하는 등의 문제도 있다.In addition, there is a method of preventing the collapse of the pattern by adding a surfactant to the developer, but this is less effective than adding a surfactant to the cleaning solution, there is also a problem such as uneven pattern size in some cases .
본 발명은 상기 종래기술의 문제점을 해결하기 위한 것으로, 현상의 마지막 단계인 잔류 포토레지스트 세정공정시에 포토레지스트 패턴의 붕괴를 방지할 목적으로 표면장력을 낮춘 새로운 조성의 포토레지스트 세정액 조성물 및 이를 이용한 패턴 형성방법을 제공하는 것을 목적으로 한다.The present invention is to solve the problems of the prior art, a photoresist cleaning liquid composition of a new composition with a lower surface tension for the purpose of preventing the collapse of the photoresist pattern during the residual photoresist cleaning process of the last stage of development and using the same It is an object to provide a pattern formation method.
상기 목적을 달성하기 위하여 본 발명에서는 물을 주성분으로 하고, 첨가제로서 하기 화학식 1로 표시되는 계면활성제를 포함하는 포토레지스트 세정액 조성물을 제공한다.In order to achieve the above object, the present invention provides a photoresist cleaning liquid composition comprising water as a main component and a surfactant represented by the following general formula (1) as an additive.
[화학식 1][Formula 1]
상기 식에서, Where
R1은 수소 또는 C1∼C5의 알킬이고,R 1 is hydrogen or C 1 -C 5 alkyl,
R2 및 R3은 C1∼C5의 알킬이며,R 2 and R 3 are C 1 -C 5 alkyl,
m은 1 내지 500 중에서 선택되는 정수이다.m is an integer selected from 1 to 500.
상기 화학식 1의 화합물의 바람직한 예로는 N,N-디메틸아크릴아마이드를 들 수 있다.Preferred examples of the compound of Formula 1 include N, N-dimethylacrylamide.
상기 화학식 1의 화합물은 포토레지스트와 물에 대한 친화력이 뛰어난 물질로서 표면장력을 감소시켜 패턴의 쓰러짐 현상을 개선할 수 있다.The compound of Formula 1 may improve the pattern collapse by reducing the surface tension as a material having excellent affinity for the photoresist and water.
본 발명의 세정액 조성물의 물은 증류수를 사용하는 것이 바람직하다.It is preferable that distilled water is used for the water of the washing | cleaning liquid composition of this invention.
상기 포토레지스트 세정액 조성물에 있어서, 계면활성제인 화학식 1의 중합체의 함량은 전체 세정액 조성물에 대해 0.001∼10중량%, 바람직하게는 0.01∼2중량%를 사용한다.In the photoresist cleaning liquid composition, the content of the polymer of Formula 1, which is a surfactant, is used in an amount of 0.001 to 10% by weight, preferably 0.01 to 2% by weight based on the total cleaning liquid composition.
상기 화학식 1의 중합체가 0.001중량% 미만으로 첨가되는 경우에는 표면장력을 낮추는 효과가 적어지므로 패턴 쓰러짐을 방지하는 효과가 낮고, 10중량%를 초과하여 첨가되는 경우에는 역시 첨가량에 비하여 표면장력을 낮추는 효과가 적어지므로 제조비용이 증가된다.When the polymer of Formula 1 is added in less than 0.001% by weight, the effect of lowering the surface tension is less, so the effect of preventing pattern collapse is low, and when added in excess of 10% by weight, the surface tension is also lowered compared to the addition amount. The effect is less, which increases the manufacturing cost.
본 발명에서는 또한 상기 세정액 조성물을 이용하는 습식현상 공정을 채택하며 하기와 같은 단계를 포함하는 포토레지스트 패턴 형성방법을 제공한다:The present invention also provides a method of forming a photoresist pattern employing a wet development process using the cleaning liquid composition and comprising the following steps:
(a) 반도체 기판에 형성된 피식각층 상부에 포토레지스트를 도포하고 소프트 베이크하여 포토레지스트 막을 형성하는 단계;(a) applying a photoresist on the etched layer formed on the semiconductor substrate and soft-baking to form a photoresist film;
(b) 상기 포토레지스트 막을 노광한 이후에 포스트 베이크하는 단계;(b) post-baking after exposing the photoresist film;
(c) 상기 포토레지스트 막을 현상액으로 현상하는 단계; 및(c) developing the photoresist film with a developer; And
(d) 상기 현상한 결과물을 본 발명에 따른 세정액 조성물로 세정하는 단계. (d) washing the developed result with the cleaning liquid composition according to the present invention.
또한, 상기 노광공정은 KrF (248nm), ArF (193nm), VUV (157nm), EUV (13nm), E-빔, X-선 또는 이온빔을 노광원으로 사용하여, 0.1 내지 50mJ/cm2의 노광에너지로 수행되는 것이 바람직하다.In addition, the exposure process is exposed to 0.1 to 50mJ / cm 2 using KrF (248nm), ArF (193nm), VUV (157nm), EUV (13nm), E-beam, X-rays or ion beam as an exposure source It is preferably carried out with energy.
한편, 상기에서 현상 단계 (c)는 알칼리 현상액을 이용하여 수행될 수 있으며, 알칼리 현상액은 0.01 내지 5중량%의 테트라메틸암모늄히드록사이드 (TMAH) 수용액인 것이 바람직하다.On the other hand, the developing step (c) in the above may be performed using an alkaline developer, the alkaline developer is preferably 0.01 to 5% by weight of tetramethylammonium hydroxide (TMAH) aqueous solution.
본 발명에서는 전술한 바와 같이, 현상의 마지막 단계에서 계면활성제인 상기 화학식 1의 화합물을 포함하는 세정액 조성물로 세정하는 공정을 거침으로써, 세정액 조성물의 표면장력이 낮아지기 때문에 포토레지스트 패턴 형성시 현상공정에서 패턴이 붕괴되는 현상을 개선시킬 수 있다.In the present invention, as described above, the surface tension of the cleaning liquid composition is lowered by going through the process of cleaning with the cleaning liquid composition containing the compound of Formula 1, which is a surfactant at the last stage of the development, in the development process when forming the photoresist pattern It can improve the collapse of the pattern.
또한, 본 발명에서는 상기 패턴 형성방법을 이용하여 제조된 반도체소자를 제공한다.In addition, the present invention provides a semiconductor device manufactured using the pattern forming method.
이하 본 발명을 실시예에 의하여 상세히 설명한다. 단 실시예는 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by examples. However, the examples are only to illustrate the invention and the present invention is not limited by the following examples.
제조예 1. 폴리(N,N-디메틸아크릴아마이드)의 합성Preparation Example 1 Synthesis of Poly (N, N-dimethylacrylamide)
N,N-디메틸아크릴아마이드 20g, AIBN 4g을 100g의 테트라하이드로퓨란 용매에 녹인 후 66℃에서 8시간 동안 반응시켰다. 반응 완료 후, 상기 용액을 디에틸에테르에서 침전을 잡아서 진공 건조하여 순수한 폴리(N,N-디메틸아크릴아마이드)를 얻었다. 상기 폴리(N,N-디메틸아크릴아마이드)의 분자량은 3,200이고, 중합체의 NMR 분석은 도 1에 도시한 바와 같다.20 g of N, N-dimethylacrylamide and 4 g of AIBN were dissolved in 100 g of tetrahydrofuran solvent and reacted at 66 ° C. for 8 hours. After completion of the reaction, the solution was precipitated in diethyl ether and dried in vacuo to obtain pure poly (N, N-dimethylacrylamide). The molecular weight of the poly (N, N- dimethyl acrylamide) is 3,200, NMR analysis of the polymer is as shown in FIG.
실시예 1. 세정액의 제조Example 1 Preparation of Washing Liquid
제조예 1에서 제조한 건조된 중합체 1g을 500g의 증류수에 녹여서 세정액을 제조하였다.1 g of the dried polymer prepared in Preparation Example 1 was dissolved in 500 g of distilled water to prepare a washing liquid.
실시예 2. 포토레지스트 패턴 형성Example 2. Photoresist Pattern Formation
헥사메틸디실라잔 (HMDS) 처리된 실리콘 웨이퍼에 피식각층을 형성시키고, 그 상부에 메타크릴레이트 타입의 감광제인 AX1020P (Clariant사)를 스핀 코팅하여 2400Å의 두께로 포토레지스트 박막을 제조한 다음, 130℃의 오븐에서 90초간 소프트 베이크 하였다. 소프트 베이크 후 ArF 레이저 노광장비로 노광하고, 130℃의 오븐에서 90초간 다시 포스트 베이크 하였다. 베이크 완료 후 2.38 중량% 테트라메틸암모늄히드록사이드 수용액에 30초간 침지하여 현상 후, 실리콘 웨이퍼를 스핀시키면서 스핀 장치의 상부로부터 실시예 1에서 제조한 세정액 300㎖를 분사시켜 세정한 후, 이를 건조시켜 미세 포토레지스트 패턴을 얻었다 (도 2 참조). 도 2에 나타낸 바와 같이 71.2nm에서 패턴 쓰러짐이 발생하여 후술하는 비교예 1에 비하여 18nm 정도의 개선 효과를 보았다.An etched layer was formed on a hexamethyldisilazane (HMDS) -treated silicon wafer, and spin-coated AX1020P (Clariant), a methacrylate-type photosensitive agent, was formed on the upper portion to prepare a photoresist thin film having a thickness of 2400 Å. Soft bake for 90 seconds in an oven at 130 ℃. After soft baking, it exposed with ArF laser exposure equipment, and post-baked again for 90 second in 130 degreeC oven. After baking, the solution was immersed in an aqueous 2.38% by weight tetramethylammonium hydroxide solution for 30 seconds, followed by development, followed by cleaning by spraying 300 ml of the cleaning solution prepared in Example 1 from the top of the spin apparatus while spinning the silicon wafer. A fine photoresist pattern was obtained (see FIG. 2). As shown in FIG. 2, pattern collapse occurred at 71.2 nm, and an improvement effect of about 18 nm was observed as compared with Comparative Example 1 described later.
비교예 1. 포토레지스트 패턴 형성Comparative Example 1. Photoresist Pattern Formation
세정액으로 실시예 1의 세정액을 사용하는 대신에 증류수를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 공정을 수행하여 포토레지스트 패턴을 얻었다 (도 3 참조). 도 3에 나타낸 바와 같이 89.2nm에서 패턴 쓰러짐이 발생하였다.A photoresist pattern was obtained in the same manner as in Example 1, except that distilled water was used instead of the cleaning solution of Example 1 as the cleaning solution (see FIG. 3). As shown in FIG. 3, pattern collapse occurred at 89.2 nm.
이상에서 살펴본 바와 같이, 본 발명의 세정액 조성물은 종래에 세정액으로 사용하던 증류수보다 표면장력이 낮기 때문에 포토레지스트 패턴 형성시, 현상의 마지막 단계에서 반도체 기판을 세정하는데 사용하면 패턴 붕괴 현상이 크게 감소함을 알 수 있었다. 따라서 본 발명의 세정액 조성물은 130nm 이하의 초미세 포토레지스트 패턴 형성 공정의 안정화에 크게 기여할 것으로 보인다. As described above, since the cleaning liquid composition of the present invention has a lower surface tension than distilled water used as a conventional cleaning liquid, when the photoresist pattern is formed, the pattern collapse phenomenon is greatly reduced when used to clean the semiconductor substrate at the end of development. And it was found. Therefore, the cleaning liquid composition of the present invention is expected to contribute greatly to the stabilization of the ultrafine photoresist pattern formation process of 130nm or less.
도 1은 본 발명의 세정액 조성물에 포함되는 중합체의 NMR 분석 그래프.1 is an NMR analysis graph of a polymer included in the cleaning liquid composition of the present invention.
도 2는 본 발명의 세정액 조성물을 이용하여 포토레지스트 패턴을 세정한 결과를 나타낸 사진.Figure 2 is a photograph showing the result of washing the photoresist pattern using the cleaning liquid composition of the present invention.
도 3은 일반적인 증류수를 사용하여 포토레지스트 패턴을 세정한 결과를 나타낸 사진.Figure 3 is a photograph showing the result of washing the photoresist pattern using a common distilled water.
Claims (7)
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