KR100772811B1 - Cleaning solution for photoresist - Google Patents
Cleaning solution for photoresist Download PDFInfo
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- KR100772811B1 KR100772811B1 KR1020010080575A KR20010080575A KR100772811B1 KR 100772811 B1 KR100772811 B1 KR 100772811B1 KR 1020010080575 A KR1020010080575 A KR 1020010080575A KR 20010080575 A KR20010080575 A KR 20010080575A KR 100772811 B1 KR100772811 B1 KR 100772811B1
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- photoresist pattern
- photoresist
- alcohol
- polyether
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 67
- 238000004140 cleaning Methods 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- -1 alcohol compound Chemical class 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 238000005406 washing Methods 0.000 claims description 5
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 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
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 28
- 239000012153 distilled water Substances 0.000 abstract description 7
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 7
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 230000007261 regionalization Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000006230 (methoxyethoxy)ethanyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- PSJBSUHYCGQTHZ-UHFFFAOYSA-N 3-Methoxy-1,2-propanediol Chemical compound COCC(O)CO PSJBSUHYCGQTHZ-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(C)[N+](*=C)[O-] Chemical compound CC(C)(C)[N+](*=C)[O-] 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000007429 general method Methods 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
- 239000011259 mixed solution Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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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)
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.
본 발명의 세정액 조성물은 하기 화학식 1의 반복 단위를 포함하는 실리콘계 계면활성제, 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 silicon-based surfactant, an alcohol compound, and water containing a repeating unit represented by the following Formula 1, and thus has a lower surface tension than distilled water. Can be improved.
[화학식 1][Formula 1]
상기 식에서,Where
a는 1∼200 중에서 선택되는 정수이고,a is an integer selected from 1 to 200,
X는 C2-C500의 폴리에테르, 알코올 또는 암모늄염이며,X is a polyether, alcohol or ammonium salt of C 2 -C 500 ,
Y는 H, CH3, C2-C500의 폴리에테르, 알코올 또는 암모늄염이다.Y is H, CH 3 , a polyether, alcohol or ammonium salt of C 2 -C 500 .
Description
도 1은 본 발명에 따른 실시예 5에 의해 형성된 포토레지스트 패턴 사진.1 is a photoresist pattern photo 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 5는 비교예에 의해 형성된 포토레지스트 패턴 사진.5 is a photoresist pattern photo formed by the comparative example.
본 발명은 포토레지스트 패턴 형성시, 현상 후 마지막 공정으로 반도체 기판을 세정하는데 사용하는 포토레지스트 세정액 조성물에 관한 것으로, 더욱 상세하게는 실리콘계 계면활성제를 포함하는 포토레지스트 세정액 조성물 및 이를 이용하여 패턴 붕괴를 방지할 수 있는 패턴을 형성하는 방법에 관한 것이다.The present invention relates to a photoresist cleaning liquid composition used to clean a semiconductor substrate in a final process after development when forming a photoresist pattern, and more particularly, a photoresist cleaning liquid composition including a silicon-based surfactant and pattern collapse using the same. It is related with the method of forming the pattern which can be prevented.
근래에 디바이스가 점점 미세화 되어감에 따라 포토레지스트 패턴의 아스펙트비 (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. do.
포토레지스트 패턴의 붕괴는 형성된 포토레지스트 패턴의 높이가 임계 높이 를 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 such 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 노광 영역의 포토레지스트 막이 현상액에 의해 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. 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.
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 있음을 알아내어 본 발명을 완성하였다.Accordingly, the present inventors can prevent the photoresist pattern collapse by using a cleaning solution of a new composition lowering the surface tension instead of distilled water in order to solve the problem that the pattern collapses in the development process when forming an ultra-fine photoresist pattern of less than 130nm. The present invention was completed by finding out.
본 발명의 목적은 포토레지스트 패턴의 붕괴를 방지할 목적으로 사용하는 새 로운 조성의 세정액 조성물을 제공하는 것이다.It is an object of the present invention to provide a cleaning composition of a new composition 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 실리콘계 계면활성제를 포함하는 세정액 조성물을 제공한다.In order to achieve the above object, the present invention provides a cleaning liquid composition comprising a silicone-based surfactant.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 우선, 하기 화학식 1의 반복단위를 포함하는 폴리에테르 변성 실리콘 화합물, 알코올 화합물 및 물을 포함하는 포토레지스트 세정액 조성물을 제공한다.In the present invention, first, a photoresist cleaning liquid composition including a polyether-modified silicone compound, an alcohol compound, and water including a repeating unit represented by Chemical Formula 1 is provided.
[화학식 1][Formula 1]
상기 식에서,Where
a는 1∼200 중에서 선택되는 정수이고,a is an integer selected from 1 to 200,
X는 C2-C500의 폴리에테르, 알코올 또는 암모늄염이며,X is a polyether, alcohol or ammonium salt of C 2 -C 500 ,
Y는 H, CH3, C2-C500의 폴리에테르, 알코올 또는 암모늄염이다.Y is H, CH 3 , a polyether, alcohol or ammonium salt of C 2 -C 500 .
상기 화학식 1의 반복단위를 포함하는 폴리에테르 변성 실리콘 화합물은 하기 화학식 1a의 화합물인 것이 바람직하다. It is preferable that the polyether modified silicone compound including the repeating unit of Formula 1 is a compound of Formula 1a.
[화학식 1a][Formula 1a]
상기 식에서,Where
m 및 n은 1∼100 중에서 선택되는 정수이고,m and n are integers selected from 1 to 100,
X는 C2-C500의 폴리에테르, 알코올 또는 암모늄염이다.X is a polyether, alcohol or ammonium salt of C 2 -C 500 .
상기 X는 하기 화학식 2의 폴리에테르, 화학식 3의 알코올 및 화학식 4a 또는 4b의 암모늄염으로 이루어진 군으로부터 선택되는 것이 바람직하다.X is preferably selected from the group consisting of polyethers of Formula 2, alcohols of Formula 3 and ammonium salts of Formula 4a or 4b.
[화학식 2][Formula 2]
-(CH2O)a(C2H4O)b(C3H6O) cR-(CH 2 O) a (C 2 H 4 O) b (C 3 H 6 O) c R
[화학식 3][Formula 3]
-CH2(CR'2)OH-CH 2 (CR ' 2 ) OH
[화학식 4a][Formula 4a]
-(CH2)dN+(R")2A- - (CH 2) d N + (R ") 2 A -
[화학식 4b][Formula 4b]
-N+(R")3A- -N + (R ") 3 A -
상기 식에서,Where
a, b 및 c는 각각 1∼100 중에서 선택되는 정수이고, a, b and c are each an integer selected from 1 to 100,
d는 1∼10 중에서 선택되는 정수이며,d is an integer selected from 1 to 10,
R, R' 및 R"는 각각 수소 또는 C1-C100의의 알킬이고,R, R 'and R "are each hydrogen or alkyl of C 1 -C 100 ,
A는 CH2COO 또는 할로겐이다.A is CH 2 COO or halogen.
상기 화학식 4a의 대표적인 예로는 -(CH2)3N+(CH3)2CH 2COO-를 들 수 있고, 화학식 4b의 대표적인 예로는 -N+(CH3)3Cl-를 들 수 있다.Representative examples of the formula 4a is - (CH 2) 3 N + (CH 3) 2 CH 2 COO - may be mentioned, a typical example of the formula 4b is -N + (CH 3) 3 Cl - can be given.
폴리에테르 변성 실리콘 중 분자량이 낮은 것은 수용액의 표면장력을 현저하게 저하시킬 수 있으며, 응고점이 낮다는 이점을 갖고 있다. 수용액의 표면장력은 pH의 영향을 받으므로, 표면장력을 저하시키는 최적의 pH에서 벗어나면 활성력이 저하되는 점에 유의해야 한다.The low molecular weight in the polyether-modified silicone can significantly lower the surface tension of the aqueous solution and has the advantage of low freezing point. Since the surface tension of the aqueous solution is affected by pH, it should be noted that the active force is deteriorated when the surface tension is departed from the optimum pH that lowers the surface tension.
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.
또한, 세정액 조성물의 물은 증류수를 사용한다.In addition, distilled water is used for the water of a washing | cleaning liquid composition.
상기 세정액 조성물에서, 폴리에테르 변성 실리콘 화합물 : 알코올 화합물 : 물의 조성비는 0.001∼5 중량% : 0.01∼10 중량% : 85∼99.989 중량%인 것이 바람 직하다.In the cleaning liquid composition, the composition ratio of polyether-modified silicone compound: alcohol compound: water is preferably 0.001 to 5% by weight: 0.01 to 10% by weight: 85 to 99.989% by weight.
본 발명에 따른 세정액 조성물은 상기 조성의 실리콘계 계면활성제, 알코올 화합물 및 물의 혼합용액을 0.2㎛ 여과기로 여과함으로써 제조될 수 있다.The cleaning liquid composition according to the present invention may be prepared by filtering a mixed solution of the silicone-based surfactant, alcohol compound and water of the above composition with a 0.2 μm 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 상기 세정액 조성물을 이용하는 포토레지스트 패턴 형성방법을 제공하는데, 그 과정은 하기와 같은 단계를 포함한다:The present invention also provides a method of forming a photoresist pattern using the cleaning liquid composition, the process 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 step is exposed to 0.1 to 50mJ / cm 2 using VUV (157nm), ArF (193nm), KrF (248nm), EUV (13nm), E-beam, X-rays or ion beams as the exposure source It is preferably carried out with energy.
한편, 상기에서 현상 단계 (c)는 알칼리 현상액을 이용하여 수행될 수 있으 며, 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 계면활성제인 폴리에테르 변성 실리콘 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 a cleaning liquid composition containing a polyether-modified silicone compound that is a surfactant in the last stage of development, so that in the developing process when forming a photoresist pattern It can improve the collapse of the pattern.
본 발명에서는 또한 상기 패턴 형성방법을 이용하여 제조된 반도체 소자를 제공한다.The present invention also provides a semiconductor device manufactured using the pattern forming method.
이하 본 발명을 실시예에 의하여 상세히 설명한다. 단 실시예는 발명을 예시하는 것일뿐 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 According to the Present Invention (1)
화학식 1a에서 X가 CH2CH2OCH2CH2OCH3인 화합물 1g, 이소프로판올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.In Formula 1a, 1 g of a compound in which X is CH 2 CH 2 OCH 2 CH 2 OCH 3 , 4 g of isopropanol, and 95 g of water was 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)
화학식 1a에서 X가 CH2CH2OH인 화합물 1g, 에탄올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.In Chemical Formula 1a, 1 g of a compound in which X is CH 2 CH 2 OH, 4 g of ethanol, and 95 g of water was 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 Compositions According to the Invention (3)
화학식 1a에서 X가 (CH2)3N+(CH3)2CH2COO -인 화합물 1g, 이소프로판올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.In Formula 1a, 1 g of a compound in which X is (CH 2 ) 3 N + (CH 3 ) 2 CH 2 COO − , isopropanol 4 g, and 95 g of water is stirred and mixed for 1 minute, followed by filtering with a 0.2 μm filter to wash the liquid according to the present invention. The composition was prepared.
실시예 4 : 본 발명에 따른 세정액 조성물 제조 (4)Example 4 Preparation of Washing Liquid Composition According to the Present Invention (4)
화학식 1a에서 X가 (CH2)3N+(CH3)2CH2COO -인 화합물 1g, 1-펜탄올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.In Formula 1a, 1 g of a compound in which X is (CH 2 ) 3 N + (CH 3 ) 2 CH 2 COO − , 1 g of 1-pentanol, and 95 g of water is stirred and mixed for 1 minute, and then filtered through a 0.2 μm filter. To prepare a cleaning liquid composition according to.
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 1 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 completion of baking after 30 seconds by dipping 2.38% by weight tetramethylammonium hydroxide aqueous developer, then spin while the silicon wafer cleaning by spraying a cleaning liquid 30㎖ prepared in Example 1 from the upper portion of the spin device, and was dried 100 nm L / S ultrafine photoresist pattern was obtained (see FIG. 1).
실시예 6 : 포토레지스트 패턴 형성 (2)Example 6 Photoresist Pattern Formation (2)
실시예 2에서 제조한 세정액을 사용하는 것을 제외하고는 실시예 5와 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 5 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 5와 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 5 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 5와 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 5, 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 5와 동일한 방법으로 포토레지스트 패턴을 얻었으나, 상기 실시예 5 내지 8에서 생성된 패턴과 달리 패턴이 붕괴되었다 (도 5 참조).A photoresist pattern was obtained in the same manner as in Example 5 except for using distilled water instead of using the cleaning solution according to the present invention, but unlike the patterns generated in Examples 5 to 8, the patterns were collapsed (FIG. 5). Reference).
이상에서 살펴본 바와 같이, 실리콘계 계면활성제인 폴리에테르 변성 실리콘 화합물, 알코올 화합물 및 물을 포함하는 본 발명의 세정액 조성물은 종래에 세정액으로 사용하던 증류수보다 표면장력이 낮기 때문에 포토레지스트 패턴 형성시, 현상 후 마지막 공정으로 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, the cleaning liquid composition of the present invention comprising a polyether-modified silicone compound, an alcohol compound, and water, which is a silicone-based surfactant, has a lower surface tension than distilled water, which is conventionally used as a cleaning liquid, so that after developing the photoresist pattern, Finally, the pattern collapse phenomenon is greatly reduced when used to clean the semiconductor substrate. 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.
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| CNB021518629A CN1240816C (en) | 2001-12-12 | 2002-12-12 | Liquid detergent for removing photoresist |
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