KR100772810B1 - Cleaning solution for photoresist - Google Patents
Cleaning solution for photoresist Download PDFInfo
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- KR100772810B1 KR100772810B1 KR1020010080574A KR20010080574A KR100772810B1 KR 100772810 B1 KR100772810 B1 KR 100772810B1 KR 1020010080574 A KR1020010080574 A KR 1020010080574A KR 20010080574 A KR20010080574 A KR 20010080574A KR 100772810 B1 KR100772810 B1 KR 100772810B1
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- photoresist
- liquid composition
- cleaning liquid
- photoresist pattern
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 66
- 238000004140 cleaning Methods 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 9
- -1 alcohol compound Chemical class 0.000 claims abstract description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- VQHSOMBJVWLPSR-JVCRWLNRSA-N lactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-JVCRWLNRSA-N 0.000 claims description 5
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- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 3
- VOIFKEWOFUNPBN-QIUUJYRFSA-N beta-D-glucuronamide Chemical compound NC(=O)[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O VOIFKEWOFUNPBN-QIUUJYRFSA-N 0.000 claims description 3
- 229950004542 glucuronamide Drugs 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010884 ion-beam technique Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims 2
- OEYNWAWWSZUGDU-UHFFFAOYSA-N 1-methoxypropane-1,2-diol Chemical compound COC(O)C(C)O OEYNWAWWSZUGDU-UHFFFAOYSA-N 0.000 claims 1
- QACUPNAKIPYZAW-RMQWDSPGSA-N O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O.O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O.O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O QACUPNAKIPYZAW-RMQWDSPGSA-N 0.000 claims 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims 1
- 239000012153 distilled water Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- 230000007261 regionalization Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- PSJBSUHYCGQTHZ-UHFFFAOYSA-N 3-Methoxy-1,2-propanediol Chemical compound COCC(O)CO PSJBSUHYCGQTHZ-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229960001031 glucose Drugs 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
- 230000007794 irritation Effects 0.000 description 1
- 229960001375 lactose Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
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
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
본 발명은 포토레지스트 세정액 조성물에 관한 것으로, 더욱 상세하게는 포토레지스트 패턴 형성시, 현상 후 마지막 공정으로 반도체 기판을 세정하는데 사용하는 포토레지스트 세정액 조성물 및 이를 이용한 패턴 형성 방법에 관한 것이다.The present invention relates to a photoresist cleaning liquid composition, and more particularly, to a photoresist cleaning liquid composition used to clean a semiconductor substrate as a final process after development, and a pattern forming method using the same, when forming a photoresist pattern.
이러한 본 발명의 세정액 조성물은 하기 화학식 1의 반복단위를 포함하는 화합물, 알코올 화합물 및 물을 포함하는 것으로 종래에 사용하던 증류수보다 표면장력이 낮기 때문에 본 발명의 세정액 조성물을 사용함으로써 패턴 붕괴 현상을 개선시킬 수 있다.The cleaning liquid composition of the present invention includes a compound, an alcohol compound, and water containing a repeating unit represented by the following Chemical Formula 1, and thus has a lower surface tension than distilled water. You can.
[화학식 1][Formula 1]
Description
도 1a는 본 발명에 따른 실시예 5에 의해 형성된 포토레지스트 패턴의 저배율 사진.Figure 1a is a low magnification photograph of a photoresist pattern formed by Example 5 according to the present invention.
도 1b는 본 발명에 따른 실시예 5에 의해 형성된 포토레지스트 패턴의 저배율 사진.Figure 1b is a low magnification photograph of the photoresist pattern formed by Example 5 according to the present invention.
도 2는 본 발명에 따른 실시예 6에 의해 형성된 포토레지스트 패턴 사진.2 is a photoresist pattern photo formed by Example 6 according to the present invention.
도 3은 본 발명에 따른 실시예 7에 의해 형성된 포토레지스트 패턴 사진.Figure 3 is a photoresist pattern photo formed by Example 7 according to the present invention.
도 4는 본 발명에 따른 실시예 8에 의해 형성된 포토레지스트 패턴 사진.Figure 4 is a photoresist pattern photo formed by Example 8 according to the present invention.
도 5a는 비교예에 의해 형성된 포토레지스트 패턴의 저배율 사진.5A is a low magnification photograph of a photoresist pattern formed by a comparative example.
도 5b는 비교예에 의해 형성된 포토레지스트 패턴의 고배율 사진.5B is a high magnification photograph of a photoresist pattern formed by a comparative example.
본 발명은 포토레지스트 세정액 조성물에 관한 것으로, 더욱 상세하게는 포토레지스트 패턴 형성시, 현상 후 마지막 공정으로 반도체 기판을 세정하는데 사용하는 포토레지스트 세정액 조성물 및 이를 이용한 패턴 형성 방법에 관한 것이다.The present invention relates to a photoresist cleaning liquid composition, and more particularly, to a photoresist cleaning liquid composition used to clean a semiconductor substrate as a final process after development, and a pattern forming method using the same, when forming a photoresist pattern.
근래에 디바이스가 점점 미세화 되어감에 따라 포토레지스트 패턴의 아스펙 트비(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, that is, 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 포토레지스트 패턴의 높이가 임계 높이를 넘었을 때 모세관력(capillary force)이 포토레지스트 자체의 탄성력을 능가하게 되어 패턴이 쓰러지게 되는 것이다. 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 is that when the height of the formed photoresist pattern exceeds the critical height, the capillary force exceeds the elastic force of the photoresist itself, causing the pattern to collapse. 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.
한편, 반도체 기판 상에 포토레지스트 패턴을 형성하는 일반적인 방법을 개략적으로 보면, 먼저 반도체 기판 상에 피식각층을 형성한 다음, 피식각층 위에 포토레지스트 막을 형성하고, 이를 노광 및 현상하여 상기 피식각층의 일부를 노출시키는 포토레지스트 패턴을 형성한다. 이때 포지티브형 포토레지스트 막을 사용한 경우에는 현상액과 포토레지스트 막의 화학 반응에 의하여 노광 영역에서 포토레지스트 막이 제거되어 포토레지스트 패턴이 형성된다.Meanwhile, when a general method of forming a photoresist pattern on a semiconductor substrate is roughly described, first, an etching target layer is formed on a semiconductor substrate, and then a photoresist film is formed on the etching target layer, and the photoresist layer is exposed and developed to expose a portion of the etching target layer. A photoresist pattern is formed to expose the film. In this case, when a positive photoresist film is used, the photoresist film is removed from the exposure area by a chemical reaction between the developer and the photoresist film to form a photoresist pattern.
상기와 같이 포토레지스트 패턴을 현상한 다음 마지막 공정으로 반도체 기판을 스핀시키면서 스핀 장치의 상부로부터 증류수를 분사시켜서 반도체 기판을 세정하는 과정을 거치는데, 이 과정에서 증류수의 표면장력이 높아 패턴이 붕괴하는 문제점이 발생한다.After developing the photoresist pattern as described above, the semiconductor substrate is cleaned by spraying distilled water from the top of the spin apparatus while spinning the semiconductor substrate. In this process, the surface tension of the distilled water is high so that the pattern collapses. A problem occurs.
이에 본 발명자들은 130nm 이하의 초미세 포토레지스트 패턴 형성시 현상공정에서 패턴이 붕괴되는 문제점을 해결하고자, 종래의 증류수 대신 표면장력을 낮춘 새로운 조성의 세정액을 사용함으로써 포토레지스트 패턴 붕괴를 방지할 수 있 음을 알아내어 본 발명을 완성하였다.Therefore, the present inventors can solve the problem of the pattern collapse in the development process when forming the ultra-fine photoresist pattern of 130nm or less, it is possible to prevent the photoresist pattern collapse by using a cleaning solution of a new composition lowering the surface tension instead of conventional distilled water. The sound was found out to complete the present invention.
본 발명의 목적은 포토레지스트 패턴의 붕괴를 방지할 목적으로 사용하는 새로운 조성의 세정액 조성물을 제공하는 것이다.An object of the present invention is to provide a cleaning liquid composition having a new composition for use for the purpose of preventing the collapse of the photoresist pattern.
또한 본 발명의 목적은 상기 세정액 조성물을 이용하여 포토레지스트 패턴을 형성하는 방법 및 이러한 방법에 의해 얻어진 반도체 소자를 제공하는 것이다.It is also an object of the present invention to provide a method of forming a photoresist pattern using the cleaning liquid composition and a semiconductor device obtained by such a method.
상기 목적을 달성하기 위하여 본 발명에서는 우선, 포토레지스트 세정액 조성물을 제공한다.In order to achieve the above object, the present invention first provides a photoresist cleaning liquid composition.
이러한 본 발명의 세정액 조성물은 하기 화학식 1의 반복단위를 포함하는 화합물, 알코올 화합물 및 물의 혼합용액을 포함한다.Such a cleaning liquid composition of the present invention comprises a mixed solution of a compound, an alcohol compound and water containing a repeating unit of the formula (1).
[화학식 1][Formula 1]
상기 화학식 1의 반복단위를 포함하는 화합물은 물에 잘 녹으며 수용액의 표면장력을 현저하게 저하시키는 역할을 하며, 아울러 독성이나 자극성이 거의 없고 입술이나 피부에 접촉되어도 장해가 일어나지 않으며 우수한 화학적 물리적 성질을 가지고 있기 때문에 표면장력을 낮추기 위한 첨가제로서 사용되기에 적합하다.The compound containing the repeating unit of Formula 1 is well soluble in water, and serves to significantly reduce the surface tension of the aqueous solution, and also has little toxicity or irritation and does not cause any trouble even when contacted with lips or skin, and has excellent chemical and physical properties. It is suitable to be used as an additive for lowering the surface tension.
상기 화학식 1의 반복단위를 포함하는 화합물의 바람직한 예로는 글루코오스(Glucose), 글루쿠론아미드(Glucuronamide), 글루쿠론산(Glucuronic acid), 수크로오스(Sucrose), 락토오스(Lactose) 또는 락티톨(Lactitol) 등을 들 수 있고, 이들을 단독으로 또는 혼합하여 사용할 수 있다.Preferred examples of the compound including the repeating unit of Formula 1 include glucose, glucuronamide, glucuronic acid, sucrose, lactose, lactitol, and lactitol. These can be mentioned, These can be used individually or in mixture.
상기 화학식 1의 반복단위를 포함하는 화합물의 사용량은 전체 세정액 조성물의 0.001 내지 5 중량%인 것이 바람직하다.The amount of the compound including the repeating unit of Formula 1 is preferably 0.001 to 5% by weight of the total cleaning liquid composition.
한편, 상기 알코올 화합물로는 C1-C10의 알킬 알코올 또는 알콕시알코올을 사용하는데, 바람직하게는 메탄올, 에탄올, 프로판올, 이소프로판올, n-부탄올, sec-부탄올, t-부탄올, 1-펜탄올, 2-펜탄올, 3-펜탄올 또는 2,2-디메틸-1-프로판올 등의 알킬 알코올을 사용하고, 2-메톡시에탄올, 2-(2-메톡시에톡시)에탄올, 1-메톡시-2-프로판 또는 3-메톡시-1,2-프로판디올 등의 알콕시알코올을 사용하며, 이들을 단독으로 또는 혼합하여 사용할 수 있다.Meanwhile, the alcohol compound may be a C 1 -C 10 alkyl alcohol or alkoxyalcohol, preferably methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, t-butanol, 1-pentanol, 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol, 1-methoxy-, using alkyl alcohols such as 2-pentanol, 3-pentanol or 2,2-dimethyl-1-propanol Alkoxy alcohols such as 2-propane or 3-methoxy-1,2-propanediol are used, and these may be used alone or in combination.
상기 알코올 화합물의 사용량은 전체 세정액 조성물의 0.01 내지 10 중량%인 것이 바람직하다.It is preferable that the usage-amount of the said alcohol compound is 0.01 to 10 weight% of the whole cleaning liquid composition.
또한 상기 물은 증류수를 말하는 것으로, 그 사용량은 전체 세정액 조성물의 85 내지 99.989 중량%인 것이 바람직하다.In addition, the water refers to distilled water, the amount is preferably 85 to 99.989% by weight of the total cleaning liquid composition.
본 발명에 따른 세정액 조성물은 이상에서 설명한 바와 같이 상기 화학식 1의 반복단위를 포함하는 화합물 0.001 내지 5 중량%, 알코올 화합물 0.01 내지 10 중량% 및 물 85 내지 99.989 중량%의 혼합용액을 만든 다음, 0.2㎛ 여과기로 여과함으로써 제조된다. As described above, the cleaning solution composition according to the present invention is prepared as a mixed solution of 0.001 to 5% by weight of the compound containing a repeating unit of Formula 1, 0.01 to 10% by weight of alcohol compound and 85 to 99.989% by weight of water, and then 0.2 It is prepared by filtration with a micrometer filter.
이러한 본 발명의 세정액 조성물은 현상액을 사용하는 즉, 습식현상 공정을 채택하는 포토레지스트 패턴 형성공정에 사용 가능하다.Such a cleaning liquid composition of the present invention can be used for a photoresist pattern forming process that uses a developer, that is, a wet development process.
본 발명에서는 또한 하기와 같은 단계를 포함하는 포토레지스트 패턴 형성방법을 제공한다:The present invention also provides a method of forming a photoresist pattern comprising the following steps:
(a) 반도체 기판에 형성된 피식각층 상부에 통상의 포토레지스트를 도포하여 포토레지스트 막을 형성하는 단계;(a) forming a photoresist film by applying a conventional photoresist on the etched layer formed on the semiconductor substrate;
(b) 상기 포토레지스트 막을 노광원으로 노광하는 단계(b) exposing the photoresist film to an exposure source
(c) 상기 노광된 포토레지스트 막을 현상액으로 현상하는 단계 ; 및(c) developing the exposed photoresist film with a developer; And
(d) 상기 결과물을 본 발명에 따른 세정액 조성물로 세정하는 단계.(d) washing the resultant with the cleaning liquid composition according to the present invention.
상기 과정에서 (b)단계의 노광전에 소프트 베이크 공정, 또는 (b)단계의 노광후에 포스트 베이크 공정을 실시하는 단계를 더 포함할 수 있으며, 이 베이크 공정은 70 내지 200℃에서 수행되는 것이 바람직하다.The process may further include a soft bake process before the exposure of step (b), or a post bake process after the exposure of step (b), which is preferably carried out at 70 to 200 ℃. .
또한, 상기 노광공정은 VUV(157nm), ArF(193nm), KrF(248nm), 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 VUV (157nm), ArF (193nm), KrF (248nm), 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 5 중량%의 테트라메틸암모늄하이드록사이드(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 상기 화학식 1의 반복단위를 포함하는 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 containing the repeating unit of Chemical Formula 1 at the end of the development, and thus developing the photoresist pattern. The phenomenon of collapse of the pattern in the process can be improved.
본 발명에서는 또한 상기 본 발명의 포토레지스트 패턴 형성방법을 이용하여 제조된 반도체 소자를 제공한다.The present invention also provides a semiconductor device manufactured using the photoresist pattern forming method of the present invention.
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.
실시예 1 : 본 발명에 따른 세정액 조성물 제조(1)Example 1 Preparation of Cleaning Liquid Composition (1) According to the Present Invention
글루코오스 0.5g, 이소프로판올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.0.5 g of glucose, 4 g of isopropanol, and 95 g of water were stirred and mixed for 1 minute, and then filtered through a 0.2 μm filter to prepare a cleaning liquid composition according to the present invention.
실시예 2 : 본 발명에 따른 세정액 조성물 제조(2)Example 2 Preparation of Washing Liquid Composition According to the Present Invention (2)
글루쿠론산 0.5g, 에탄올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.0.5 g of glucuronic acid, 4 g of ethanol, and 95 g of water were stirred and mixed for 1 minute, and then filtered through a 0.2 μm filter to prepare a cleaning liquid composition according to the present invention.
실시예 3 : 본 발명에 따른 세정액 조성물 제조(3)Example 3 Preparation of Cleaning Liquid Composition (3) According to the Present Invention
락토오스 0.5g, 이소프로판올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.0.5 g of lactose, 4 g of isopropanol, and 95 g of water were stirred and mixed for 1 minute, and then filtered through a 0.2 μm filter to prepare a cleaning liquid composition according to the present invention.
실시예 4 : 본 발명에 따른 세정액 조성물 제조(4)Example 4 Preparation of Cleaning Liquid Composition (4) According to the Present Invention
락티톨 0.5g, 1-펜탄올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.0.5 g of lactitol, 4 g of 1-pentanol, and 95 g of water were stirred and mixed for 1 minute, and then filtered through a 0.2 μm filter to prepare a cleaning liquid composition according to the present invention.
실시예 5 : 포토레지스트 패턴 형성(1)Example 5 Photoresist Pattern Formation (1)
헥사메틸디실라잔(HMDS) 처리된 실리콘 웨이퍼에 피식각층을 형성시키고, 그 상부에 메타크릴레이트 타입의 감광제인 Clariant사의 AX1020P를 3000rpm으로 스핀 코팅하여 포토레지스트 박막을 제조한 다음, 120℃의 오븐에서 90초간 소프트 베이크 하였다. 소프트 베이크 후 ArF 레이저 노광장비로 노광하고, 120℃의 오븐에서 90초간 다시 포스트 베이크 하였다. 베이크 완료후 2.38 중량% 테트라메틸암모늄하이드록사이드 수용액에 30초간 침지하여 현상 후, 실리콘 웨이퍼를 스핀시키면서 스핀 장치의 상부로부터 실시예 1에서 제조한 세정액 30㎖를 분사시켜 세정한 후, 이를 건조시켜 100㎚ L/S 초미세 포토레지스트 패턴을 얻었다(도 1a 및 도 1b 참조).An etched layer was formed on a hexamethyldisilazane (HMDS) -treated silicon wafer, and a photoresist thin film was prepared by spin-coating a methacrylate-type photosensitive agent Clariant's AX1020P at 3000 rpm, followed by an oven at 120 ° C. Soft bake for 90 seconds at. After soft baking, it exposed with the ArF laser exposure equipment, and post-baked again for 90 second in 120 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 washing with 30 ml of the cleaning solution prepared in Example 1 from the top of the spin apparatus while spinning the silicon wafer, followed by drying. A 100 nm L / S ultrafine photoresist pattern was obtained (see FIGS. 1A and 1B).
실시예 6 : 포토레지스트 패턴 형성(2)Example 6 Photoresist Pattern Formation (2)
실시예 2에서 제조한 세정액을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 100㎚ L/S 초미세 포토레지스트 패턴을 얻었다(도 2 참조). A 100 nm L / S ultrafine photoresist pattern was obtained in the same manner as in Example 1 except that the cleaning solution prepared in Example 2 was used (see FIG. 2).
실시예 7 : 포토레지스트 패턴 형성(3)Example 7 Photoresist Pattern Formation (3)
실시예 3에서 제조한 세정액을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 100㎚ L/S 초미세 포토레지스트 패턴을 얻었다(도 3 참조). A 100 nm L / S ultrafine photoresist pattern was obtained in the same manner as in Example 1, except that the cleaning solution prepared in Example 3 was used (see FIG. 3).
실시예 8 : 포토레지스트 패턴 형성(4)Example 8 Photoresist Pattern Formation (4)
실시예 4에서 제조한 세정액을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 100㎚ L/S 초미세 포토레지스트 패턴을 얻었다(도 4 참조).A 100 nm L / S ultrafine photoresist pattern was obtained in the same manner as in Example 1 except that the cleaning solution prepared in Example 4 was used (see FIG. 4).
비교예 : 포토레지스트 패턴 형성(5)Comparative Example: Forming Photoresist Pattern (5)
본 발명에 따른 세정액을 사용하는 대신 증류수를 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 100㎚ L/S 초미세 포토레지스트 패턴을 얻었으나, 상기 실시예 5 내지 8에서 생성된 패턴과 달리 패턴이 붕괴되었다(도 5a 및 도 5b 참조).A 100 nm L / S ultrafine photoresist pattern was obtained in the same manner as in Example 1 except that distilled water was used instead of the cleaning solution according to the present invention. However, unlike the patterns generated in Examples 5 to 8, The pattern collapsed (see FIGS. 5A and 5B).
이상에서 살펴본 바와 같이, 상기 화학식 1의 반복단위를 포함하는 화합물, 알코올 화합물 및 물을 포함하는 본 발명의 세정액 조성물은 종래에 사용하던 증류수보다 표면장력이 낮기 때문에 포토레지스트 패턴 형성시, 현상 후 마지막 공정으로 반도체 기판을 세정하는데 사용함으로써 패턴 붕괴 현상이 크게 줄어듬을 알 수 있었다. 따라서 130nm 이하의 초미세 포토레지스트 패턴 형성 공정의 안정화에 크게 기여할 것으로 보인다.As described above, the cleaning liquid composition of the present invention comprising a compound, an alcohol compound, and water containing the repeating unit of Formula 1 has a lower surface tension than distilled water, which is conventionally used. It was found that the pattern collapse phenomenon was greatly reduced by using the semiconductor substrate to clean the process. Therefore, it is expected to contribute greatly to the stabilization of the ultrafine photoresist pattern formation process of 130 nm or less.
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| KR1020010080574A KR100772810B1 (en) | 2001-12-18 | 2001-12-18 | Cleaning solution for photoresist |
| CNB021518629A CN1240816C (en) | 2001-12-12 | 2002-12-12 | Liquid detergent for removing photoresist |
| US10/317,578 US7563753B2 (en) | 2001-12-12 | 2002-12-12 | Cleaning solution for removing photoresist |
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| JP2906590B2 (en) * | 1990-06-14 | 1999-06-21 | 三菱瓦斯化学株式会社 | Surface treatment agent for aluminum wiring semiconductor substrate |
| WO2000003306A1 (en) * | 1998-07-10 | 2000-01-20 | Clariant International, Ltd. | Composition for stripping photoresist and organic materials from substrate surfaces |
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| JP2906590B2 (en) * | 1990-06-14 | 1999-06-21 | 三菱瓦斯化学株式会社 | Surface treatment agent for aluminum wiring semiconductor substrate |
| WO2000003306A1 (en) * | 1998-07-10 | 2000-01-20 | Clariant International, Ltd. | Composition for stripping photoresist and organic materials from substrate surfaces |
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