KR20120135958A - Cleaning composition for photolithography and method for forming photoresist fine pattern using the same - Google Patents

Cleaning composition for photolithography and method for forming photoresist fine pattern using the same Download PDF

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KR20120135958A
KR20120135958A KR1020110054873A KR20110054873A KR20120135958A KR 20120135958 A KR20120135958 A KR 20120135958A KR 1020110054873 A KR1020110054873 A KR 1020110054873A KR 20110054873 A KR20110054873 A KR 20110054873A KR 20120135958 A KR20120135958 A KR 20120135958A
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formula
cleaning liquid
liquid composition
photolithography
pattern
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KR101863636B1 (en
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오승근
이재우
김재현
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주식회사 동진쎄미켐
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • 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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

PURPOSE: A cleaning liquid composition for photolithography and a photoresist micropattern forming method using the same are provided to efficiently form micropatterns by reduce the hole sizes of photoresist patterns by including an ionic compound. CONSTITUTION: A cleaning liquid composition includes an ionic compound and a solvent. The ionic compound is selected from a compound represented by chemical formula 1, a compound represented by chemical formula 2, and the mixture of the compounds. In chemical formulas, R1 and R2 are hydrogen atoms or substituted or non-substituted C1-25 hydrocarbon groups. A photoresist micropattern forming method includes the following steps: a photoresist layer is formed on a semiconductor substrate; photoresist patterns are formed by exposing the developing the photoresist layer; the photoresist patterns are cleaned with the cleaning liquid composition; and the cleaned photoresist patterns are dried and hard baked to reduce the hole sizes of the patterns.

Description

포토리소그래피용 세정액 조성물 및 이를 이용한 포토레지스트 미세패턴 형성방법{Cleaning composition for photolithography and method for forming photoresist fine pattern using the same}Cleaning composition for photolithography and method for forming photoresist fine pattern using the same}

본 발명은 세정액 조성물에 관한 것으로서, 더욱 상세하게는, 콘택트 홀 패턴 형성 공정에서, 패턴 세정 및 세정 후 가열에 의해 콘택트 홀 패턴의 크기를 축소시킬 수 있는 포토리소그래피용 세정액 조성물 및 이를 이용한 포토레지스트 미세패턴 형성방법에 관한 것이다.
The present invention relates to a cleaning liquid composition, and more particularly, in a contact hole pattern forming process, a cleaning liquid composition for photolithography capable of reducing the size of a contact hole pattern by pattern cleaning and heating after cleaning and a photoresist fine using the same It relates to a pattern forming method.

반도체 디바이스의 소형화 및 집적화에 수반하여, 반도체 디바이스의 제조에 사용되는 레지스트 재료도 이와 같은 소형화 및 집적화에 대응할 수 있도록 개량되어 왔다. 또한, 반도체 고집적도에 따른 미세패턴 구현을 위해서 노광원의 파장이 13.4nm인 극자외선 리소그라피(extreme ultraviolet lithography: EUVL) 기술이 이용되고 있다. 노광원의 파장이 작아짐에 따라, 한계 해상력의 크기가 점차 작아지고 있지만, 궁극적으로 도달하고자 하는 패턴 사이즈에 도달하기에는 기술적인 어려움이 많이 남아 있다.With the miniaturization and integration of semiconductor devices, resist materials used in the manufacture of semiconductor devices have also been improved to cope with such miniaturization and integration. In addition, extreme ultraviolet lithography (EUVL) technology having a wavelength of 13.4 nm as an exposure source is used to realize a fine pattern according to semiconductor high integration. As the wavelength of the exposure source decreases, the magnitude of the limit resolution gradually decreases, but technical difficulties remain in reaching the pattern size ultimately desired to reach.

특히, 노광원의 빛 정보가 적은 다크 필드(dark filed) 영역의 콘택트 홀(Contact Hole) 패턴 해상 시 큰 어려움이 있으며, 이를 극복하기 위해서 여러 가지 패턴 수축(pattern shrink) 기술이 개발되었다.
In particular, there is a great difficulty in resolving a contact hole pattern in a dark filed region where light information of an exposure source is low, and various pattern shrink technologies have been developed to overcome this problem.

대한민국 공개특허 10-2009-0082232호, 대한민국 공개특허 10-2010-0047229호, 대한민국 공개특허 10-2010-0014642호, 및 대한민국 공개특허 10-2008-0014388호에는 패턴이 완성된 기판 위에 새로운 코팅막을 형성시켜 화학적으로 콘택트 홀(Contact hole) 패턴의 수축(shrink), 즉, 홀 크기를 줄이는 방법들이 개시되어 있다. 그러나, 이러한 방법들은 코팅막 형성에 따른 추가적인 공정이 많이 추가되므로, 생산성 및 비용적인 측면에서 불리하다는 단점이 있다.
Republic of Korea Patent Publication No. 10-2009-0082232, Republic of Korea Patent Publication 10-2010-0047229, Republic of Korea Patent Publication 10-2010-0014642, and Republic of Korea Patent Publication No. 10-2008-0014388 a new coating film on a patterned substrate Methods of forming and chemically shrinking contact hole patterns, ie, reducing hole size, are disclosed. However, these methods have a disadvantage in that they are disadvantageous in terms of productivity and cost since many additional processes according to the coating film are added.

따라서, 본 발명의 목적은, 패턴 세정 및 세정 후 가열 과정으로 콘택트 홀 패턴의 홀 크기를 축소할 수 있는 포토리소그래피용 세정액 조성물 및 이를 이용한 포토레지스트 미세패턴 형성방법을 제공하는 것이다.
Accordingly, it is an object of the present invention to reduce the hole size of a contact hole pattern by pattern cleaning and post-cleaning heating. It is to provide a cleaning liquid composition for photolithography and a method of forming a photoresist fine pattern using the same.

상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 화합물, 하기 화학식 2로 표시되는 화합물 및 이들의 혼합물로 이루어진 군으로부터 선택되는 이온성 화합물; 및 용매를 포함하는 포토리소그래피용 세정액 조성물을 제공한다.In order to achieve the above object, the present invention is an ionic compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2) and mixtures thereof; And it provides a cleaning liquid composition for photolithography comprising a solvent.

[화학식 1] [Formula 1]

Figure pat00001
Figure pat00001

[화학식 2] [Formula 2]

Figure pat00002
Figure pat00002

상기 화학식 1 및 2에서, R1 및 R2는 각각 독립적으로 수소 원자(H), 또는 치환 또는 비치환된 탄소수 1 내지 25의 탄화수소기이다.
In Formulas 1 and 2, R 1 and R 2 are each independently a hydrogen atom (H) or a substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms.

또한, 본 발명은, 피식각층이 형성된 반도체 기판 상에 포토레지스트막을 형성하는 단계; 상기 포토레지스트막을 노광 및 현상하여 포토레지스트 패턴(콘택트 홀 패턴)을 형성하는 단계; 상기 포토레지스트 패턴을 상기 포토리소그래피용 세정액 조성물로 세정하는 단계; 및 상기 세정된 포토레지스트 패턴을 건조하고, 110 내지 180℃로 가열(하드 베이크)하여, 패턴의 홀 크기를 수축시키는 단계를 포함하는 포토레지스트 미세패턴 형성 방법을 제공한다.
The present invention also provides a method for forming a photoresist film on a semiconductor substrate on which an etched layer is formed; Exposing and developing the photoresist film to form a photoresist pattern (contact hole pattern); Washing the photoresist pattern with the cleaning liquid composition for photolithography; And drying the cleaned photoresist pattern and heating (hard baking) to 110 to 180 ° C. to shrink the hole size of the pattern.

본 발명에 따른 포토리소그래피용 세정액 조성물은, 이온성 화합물을 포함하는 것으로서, 패턴 세정 및 세정 후 가열(110 내지 180℃) 과정을 통하여 포토레지스트 패턴(콘택트 홀 패턴)의 홀 크기를 줄일(shrink) 수 있어, 미세패턴 형성에 유용하다.
The cleaning liquid composition for photolithography according to the present invention includes an ionic compound and shrinks the hole size of the photoresist pattern (contact hole pattern) through a pattern cleaning and heating after cleaning (110 to 180 ° C.). It can be used to form a fine pattern.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명에 따른 포토리소그래피용 세정액 조성물은 하기 화학식 1로 표시되는 화합물, 하기 화학식 2로 표시되는 화합물 및 이들의 혼합물로 이루어진 군으로부터 선택되는 이온성 화합물, 및 용매를 포함한다.The cleaning liquid composition for photolithography according to the present invention includes an ionic compound selected from the group consisting of a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, and a mixture thereof, and a solvent.

Figure pat00003
Figure pat00003

Figure pat00004
Figure pat00004

상기 화학식 1 및 2에서, R1 및 R2는 각각 독립적으로 수소 원자(H), 또는 치환 또는 비치환된 탄소수 1 내지 25의 탄화수소기, 바람직하게는 산소 원자(O), 질소 원자(N), 황 원자(S) 등의 헤테로 원자로 치환되거나 치환되지 않은 탄소수 1 내지 20의 탄화수소기(예를 들면, 알킬기, 히드록시알킬기, 벤질알콜기, 이미다졸기 등)이고, 예를 들면, 옥틸기, 노닐기, 데실기, 라우릴기, 펜타데실기, 미리스틸기, 팔미틸기, 스테아릴기 등을 예시할 수 있다.
In Formulas 1 and 2, R 1 and R 2 are each independently a hydrogen atom (H), or a substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms, preferably an oxygen atom (O), a nitrogen atom (N) , A hydrocarbon group having 1 to 20 carbon atoms (for example, an alkyl group, a hydroxyalkyl group, a benzyl alcohol group, an imidazole group, etc.) unsubstituted or substituted with a hetero atom such as a sulfur atom (S), for example, an octyl group , Nonyl group, decyl group, lauryl group, pentadecyl group, myristyl group, palmityl group, stearyl group and the like.

본 발명에 사용되는 이온성 화합물은, 세정 시 포토레지스트 패턴 표면에 흡착되고, 가열(하드 베이크) 과정에서 고분자 가소제 역할을 하여 포토레지스트 조성물(감광성 고분자)의 유리전이온도(Tg)를 낮춰줄 수 있는 것으로서, 상기 화학식 1 및/또는 2의 제품화 되어있는 이온성 화합물을 사용할 수도 있다. 상기 이온성 화합물의 함량은, 전체 포토리소그래피용 세정액 조성물에 대하여, 0.001 내지 5중량%, 바람직하게는 0.005 내지 1중량%, 더욱 바람직하게는 0.01 내지 0.5중량%, 가장 바람직하게는 0.05 내지 0.1중량%이다. 상기 이온성 화합물의 함량이 0.001중량% 미만이면, 패턴 수축(shrink) 기능을 나타내지 않을 우려가 있고, 5중량%를 초과하면, 특별한 장점은 없으며, 불순물로 작용할 우려가 있다.
The ionic compound used in the present invention is adsorbed on the surface of the photoresist pattern during cleaning, and acts as a plasticizer during heating (hard bake) to lower the glass transition temperature (Tg) of the photoresist composition (photosensitive polymer). As present, ionic compounds commercialized in the above formulas (1) and / or (2) may be used. The content of the ionic compound is 0.001 to 5% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0.5% by weight, most preferably 0.05 to 0.1% by weight based on the total cleaning liquid composition for photolithography. %to be. If the content of the ionic compound is less than 0.001% by weight, the pattern shrinkage function may not be exhibited. If the content of the ionic compound is more than 5% by weight, there is no particular advantage, and it may act as an impurity.

상기 화학식 1로 표시되는 이온성 화합물의 대표적인 예로는, 하기 화학식 1a 내지 1g로 표시되는 이온성 화합물을 예시할 수 있다.Representative examples of the ionic compound represented by Chemical Formula 1 may include an ionic compound represented by the following Chemical Formulas 1a to 1g.

[화학식 1a][Formula 1a]

Figure pat00005
Figure pat00005

[화학식 1b][Chemical Formula 1b]

Figure pat00006
Figure pat00006

[화학식 1c][Chemical Formula 1c]

Figure pat00007
Figure pat00007

[화학식 1d]≪ RTI ID = 0.0 &

Figure pat00008
Figure pat00008

[화학식 1e][Formula 1e]

Figure pat00009
Figure pat00009

[화학식 1f](1f)

Figure pat00010
Figure pat00010

[화학식 1g][Formula 1g]

Figure pat00011

Figure pat00011

상기 화학식 2로 표시되는 이온성 화합물의 대표적인 예로는, 하기 화학식 2a 내지 2i로 표시되는 이온성 화합물을 예시할 수 있다.Representative examples of the ionic compound represented by Formula 2 may include an ionic compound represented by the following Formulas 2a to 2i.

[화학식 2a](2a)

Figure pat00012
Figure pat00012

[화학식 2b][Formula 2b]

Figure pat00013
Figure pat00013

[화학식 2c][Formula 2c]

Figure pat00014
Figure pat00014

[화학식 2d](2d)

Figure pat00015
Figure pat00015

[화학식 2e][Formula 2e]

Figure pat00016
Figure pat00016

[화학식 2f](2f)

Figure pat00017
Figure pat00017

[화학식 2g][Chemical Formula 2g]

Figure pat00018
Figure pat00018

[화학식 2h][Chemical Formula 2h]

Figure pat00019
Figure pat00019

[화학식 2i][Formula 2i]

Figure pat00020

Figure pat00020

본 발명에 사용되는 용매는, 포토레지스트 패턴을 세정하기 위한 것으로서, 물(순수(pure water)), 유기 용매 또는 물과 유기 용매를 혼합한 혼합 용매를 사용할 수 있다. 예를 들면, 포지티브 톤 현상(positive tone development: PTD) 공정 사용 시, 상기 용매로는 물, 1가(價) 또는 다가(多價) 알코올계 유기 용매, 또는 이들의 혼합 용매를 사용할 수 있으며, 상기 1가 알코올로는 메탄올, 에탄올, 프로판올, 이소프로필 알코올(isopropyl alcohol: IPA) 등을 예시할 수 있고, 상기 다가 알코올로는 에틸렌글리콜, 프로필렌글리콜, 디에틸렌글리콜, 글리세린, 이들의 알킬에테르화물 또는 에스테르화물 등을 예시할 수 있다. 또한, 네가티브 톤 현상(negative tone development: NTD) 공정 사용 시, 상기 용매로는 지용성 알코올 용매(부탄올, 헥산올, 헵탄올, 옥탄올 등)을 단독으로 사용할 수 있다.The solvent used for this invention is for washing a photoresist pattern, and can use water (pure water), an organic solvent, or a mixed solvent which mixed water and an organic solvent. For example, when using a positive tone development (PTD) process, water, a monohydric or polyhydric alcohol-based organic solvent, or a mixed solvent thereof may be used as the solvent. Examples of the monohydric alcohol include methanol, ethanol, propanol, and isopropyl alcohol (IPA). Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, glycerin, and alkyl ether compounds thereof. Or esterified etc. can be illustrated. In addition, when a negative tone development (NTD) process is used, the solvent may be a fat-soluble alcohol solvent (butanol, hexanol, heptanol, octanol, etc.) alone.

상기 용매의 함량은 전체 포토리소그래피용 세정액 조성물에 대하여 상기 이온성 화합물을 제외한 나머지 성분이며, PTD 공정 사용 시, 혼합 용매를 사용할 경우, 상기 알코올계 유기 용매의 함량은, 전체 혼합 용매에 대하여, 0.01 내지 50중량%, 바람직하게는 0.1 내지 20중량%이다. 상기 혼합 용매 사용 시, 상기 수용성 알코올계 유기 용매의 함량이 전체 혼합 용매에 대하여 50중량%를 초과하면, 용매에 포토레지스트 패턴이 용해되어 패턴 왜곡 현상이 나타날 우려가 있다.
The content of the solvent is the remaining components except for the ionic compound with respect to the cleaning liquid composition for the entire photolithography, when using a mixed solvent in the PTD process, the content of the alcohol-based organic solvent, 0.01 to the total mixed solvent, To 50% by weight, preferably 0.1 to 20% by weight. When using the mixed solvent, if the content of the water-soluble alcohol-based organic solvent exceeds 50% by weight relative to the total mixed solvent, the photoresist pattern is dissolved in the solvent may cause a pattern distortion phenomenon.

본 발명에 따른 포토리소그래피용 세정액 조성물은, 필요에 따라, 계면활성제 등의 첨가물을 더욱 포함할 수 있다.The washing | cleaning liquid composition for photolithography which concerns on this invention can further contain additives, such as surfactant, as needed.

상기 계면활성제로는 통상적인 계면활성제를 제한 없이 사용할 수 있으며, 예를 들면, 전체 포토리소그래피용 세정액 조성물 100중량부에 대하여, 0.001 내지 5중량부, 바람직하게는 0.005 내지 1중량부, 더욱 바람직하게는 0.01 내지 0.5중량부, 가장 바람직하게는 0.01 내지 0.1중량부의 계면활성제를 사용할 수 있다.
As the surfactant, a conventional surfactant can be used without limitation, for example, 0.001 to 5 parts by weight, preferably 0.005 to 1 part by weight, more preferably based on 100 parts by weight of the total cleaning liquid composition for photolithography. 0.01 to 0.5 parts by weight, most preferably 0.01 to 0.1 part by weight of the surfactant can be used.

본 발명에 따른 세정액 조성물은, 통상적인 포토리소그래피 공정의 세정 공정에 사용될 수 있으며, 패턴 세정 후 가열 과정을 통해 형성된 포토레지스트 패턴(콘택트 홀 패턴)의 홀 크기를 수축시킴으로써, 미세 패턴을 형성할 수 있다. 예를 들어, 본 발명에 따른 포토레지스트 미세패턴 형성 방법은, (a) 피식각층이 형성된 반도체 기판 상에 포토레지스트막을 형성하는 단계, (b) 상기 포토레지스트막을 노광 및 현상하여 포토레지스트 패턴(콘택트 홀 패턴)을 형성하는 단계, (c) 상기 포토레지스트 패턴을 상기 포토리소그래피용 세정액 조성물로 세정하는 단계, 및 (d) 상기 세정된 포토레지스트 패턴을 스핀 아웃(spin out, 스핀 드라이(spin dry)) 등의 방법으로 건조하고, 110 내지 180℃, 바람직하게는 115 내지 150℃로 가열(하드 베이크(hard bake))하여, 패턴의 홀 크기를 수축시키는 단계를 포함할 수 있다.
The cleaning liquid composition according to the present invention can be used in the cleaning process of a conventional photolithography process, and by shrinking the hole size of the photoresist pattern (contact hole pattern) formed through heating after pattern cleaning, a fine pattern can be formed. have. For example, a method of forming a photoresist micropattern according to the present invention may include (a) forming a photoresist film on a semiconductor substrate on which an etched layer is formed, and (b) exposing and developing the photoresist film to form a photoresist pattern (contact). Hole pattern), (c) washing the photoresist pattern with the cleaning liquid composition for photolithography, and (d) spin out, spin dry the cleaned photoresist pattern. Drying), and heating (hard bake) to 110 to 180 ° C, preferably 115 to 150 ° C, to shrink the hole size of the pattern.

상기 포토레지스트 미세패턴 형성 방법에서, 상기 포토레지스트막 및 패턴 형성을 위한 포토레지스트 조성물로는 통상의 포토레지스트 조성물(예를 들면, 하기 실시예 및 비교예의 포토레지스트 조성물)을 제한 없이 사용할 수 있고, 포토레지스트 패턴의 세정은 순수를 이용한 1차 세정 후, 본 발명의 세정액 조성물에 의한 2차 세정에 의한 것일 수 있으며, 상기 가열(하드 베이크) 과정 시, 가열 온도가 110℃ 미만이면, 패턴의 홀 크기를 효과적으로 수축시키지 못할 우려가 있고, 가열 온도가 180℃를 초과하면, 포토레지스트에 사용된 고분자의 분해에 의해 패턴이 왜곡될 우려가 있다.
In the photoresist micropattern forming method, as a photoresist composition for forming the photoresist film and the pattern, conventional photoresist compositions (eg, photoresist compositions of Examples and Comparative Examples below) may be used without limitation, The cleaning of the photoresist pattern may be by secondary cleaning with the cleaning liquid composition of the present invention after the first cleaning using pure water, and in the heating (hard bake) process, if the heating temperature is less than 110 ° C, the hole of the pattern There is a fear that the size cannot be effectively shrunk, and if the heating temperature exceeds 180 ° C, the pattern may be distorted due to decomposition of the polymer used in the photoresist.

이하, 구체적인 실시예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 예시하기 위한 것으로서, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention.

A. 포토리소그래피용 세정액 조성물의 제조 A. Preparation of Cleaning Liquid Composition for Photolithography

하기 표 1 내지 3의 조성에 따라, 각각의 화학식을 갖는 제품화된 이온성 화합물(알드리치사, TCI사 제품) 및 용매를 4시간 동안 혼합하여, 이온성 화합물을 용매에 완전히 용해시킨 후, 0.1㎛ 크기의 기공을 갖는 필터로 여과하여 포토리소그래피용 세정액 조성물을 제조하였다.
According to the composition of Tables 1 to 3, a commercialized ionic compound (Aldrich, manufactured by TCI, Inc.) and a solvent having each formula were mixed for 4 hours, and the ionic compound was completely dissolved in the solvent, and then 0.1 μm. The filter composition having pores of the size was filtered to prepare a cleaning liquid composition for photolithography.

B. 포토레지스트 패턴 형성 및 세정액 조성물의 평가 B. Formation of Photoresist Pattern and Evaluation of Cleaning Liquid Composition

(a) 포토레지스트 패턴 형성 및 세정액 조성물 평가를 위하여, 다음과 같이 감광성 고분자를 합성하였다. 2-메틸-2-아다만틸 메타크릴레이트(2-methyl-2-adamantyl methacrylate) 117.2g(0.5mol), 3-히드록시-1-아다만틸 메타크릴레이트(3-hydroxy-1-adamantyl methacrylate) 23.6g(0.1mol), 2-옥소테트라하이드로퓨란-2-일 메타아크릴레이트(2-oxotetrahydrofuran-3-yl methacrylate) 68.0g(0.4mol) 및 아조비스(이소부티로니트릴)(AIBN) 6.6g을 무수 테트라히드로퓨란(tetrahydrofuran: THF) 125g에 용해시키고, 동결방법으로 앰플(ampoule)을 사용하여 가스를 제거한 다음, 반응물을 68℃에서 24시간 동안 중합시켰다.　중합이 완결된 후, 과량의 디에틸에테르에 반응 용액을 천천히 떨어뜨려 침전시키고, 침전물을 다시 테트라히드로퓨란(THF)에 용해시킨 후, 디에틸에테르에 재침전시켜 포토레지스트용 감광성 고분자(terpolymer)를 얻었다(수율: 53%, 중량평균분자량(Mw): 8,500, 다분산지수(PDI): 1.8).
(a) For forming the photoresist pattern and evaluating the cleaning liquid composition, a photosensitive polymer was synthesized as follows. 117.2 g (0.5 mol) 2-methyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate (3-hydroxy-1-adamantyl 23.6 g (0.1 mol) methacrylate, 68.0 g (0.4 mol) 2-oxotetrahydrofuran-3-yl methacrylate and azobis (isobutyronitrile) (AIBN) 6.6 g was dissolved in 125 g of anhydrous tetrahydrofuran (THF), degassed using an ampoule by the freezing method, and the reaction was then polymerized at 68 ° C. for 24 hours. After the polymerization was completed, the reaction solution was slowly dropped into excess diethyl ether to precipitate, and the precipitate was dissolved in tetrahydrofuran (THF) again, and then precipitated again in diethyl ether to form a photosensitive terpolymer for photoresist. (Yield: 53%, weight average molecular weight (Mw): 8,500, polydispersity index (PDI): 1.8).

(b) 다음으로, 상기 (a)에서 합성한 감광성 고분자, 광산발생제로서, 상기 감광성 고분자 100중량부에 대하여 10중량부의 디페닐파라톨루에닐설포늄 노나플레이트(TPS-NF), 염기 안정제(quencher)로서, 상기 광산발생제 100중량부에 대하여 20중량부의 트리에탄올아민을 프로필렌글리콜모노메틸에테르아세테이트(PGMEA)에 넣고 12시간 이상 교반하여 완전히 녹인 후, 0.01㎛ 크기의 기공을 갖는 나일론 재질 필터 및 폴리테트라플루오로에틸렌(polytetrafluoroethylene: PTFE) 재질 필터에 순차적으로 여과시켜, 포토레지스트 조성물을 제조하였다.
(b) Next, as the photosensitive polymer synthesized in the above (a), a photoacid generator, 10 parts by weight of diphenyl paratoluenylsulfonium nona plate (TPS-NF), base stabilizer (to 100 parts by weight of the photosensitive polymer) quencher), 20 parts by weight of triethanolamine based on 100 parts by weight of the photoacid generator is added to propylene glycol monomethyl ether acetate (PGMEA) and stirred for at least 12 hours to completely dissolve, and then a nylon filter having pores having a size of 0.01 μm. The photoresist composition was prepared by filtration sequentially through a polytetrafluoroethylene (PTFE) material filter.

(c) 상기 (b)에서 제조된 포토레지스트 조성물을, 실리콘 웨이퍼의 피식각층 상부에 스핀 코팅하여, 포토레지스트 박막(필름)을 형성한 다음, 100℃에서 60초 동안 가열(프리베이킹(prebaking))하고, 소정의 (다크 필드(dark field)) 포토마스크를 사용하여, (i) 개구수(Numerical Aperture: N.A.) 0.85인 ArF ASML 1200B 장비로 노광하거나(실시예 1 내지 24, 비교예 1 내지 2), (ii) 극자외선 리소그라피(extreme ultraviolet lithography: EUVL) 노광기로 노광(실시예 25 내지 26, 비교예 3 내지 4)한 다음, 125℃에서 60초 동안 가열(post exposure bake: PEB)하였다. 이렇게 베이크(가열)한 웨이퍼를 2.38중량%의 테트라메틸암모늄히드록사이드(TMAH) 수용액으로 30초간 현상함으로써(PTD 공정 사용), (i) 필름 두께 140nm, 홀 구경 100nm 의 1 : 1 콘택트 홀(Contact Hole) 패턴(비교예 1) 또는 (ii) 필름 두께 60nm, 홀 구경 30nm 의 1 : 1 콘택트 홀(Contact Hole) 패턴(비교예 3)을 형성하였다. 또한, 세정액 조성물에 의한 세정 없이, 상기 현상된 패턴을 110 내지 180℃에서 가열(하드 베이크)하여 (i) 필름 두께 140nm, 홀 구경 100nm 의 1 : 1 콘택트 홀(Contact Hole) 패턴(비교예 2) 또는 (ii) 필름 두께 60nm, 홀 구경 30nm 의 1 : 1 콘택트 홀(Contact Hole) 패턴(비교예 4)을 형성하였다. 상기 패턴의 홀 구경 크기는 전자현미경(Critical Dimension Scanning Electron Microscope: CD-SEM, 제조사: Hitachi, 장치명: S9220)를 사용하여 측정하였다.
(c) spin coating the photoresist composition prepared in (b) on the etched layer of the silicon wafer to form a photoresist thin film (film), and then heating (prebaking) at 100 ° C. for 60 seconds. Using a predetermined (dark field) photomask, and (i) exposed to ArF ASML 1200B equipment having a numerical aperture (NA) of 0.85 (Examples 1 to 24, Comparative Examples 1 to 1). 2), (ii) exposure with an extreme ultraviolet lithography (EUVL) exposure machine (Examples 25 to 26, Comparative Examples 3 to 4), and then heated at 125 ° C. for 60 seconds (post exposure bake: PEB). . This baked (heated) wafer was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds (using the PDT process), thereby (i) 1: 1 contact holes having a film thickness of 140 nm and a hole diameter of 100 nm. Contact Hole pattern (Comparative Example 1) or (ii) A 1: 1 contact hole pattern (Comparative Example 3) having a film thickness of 60 nm and a hole diameter of 30 nm was formed. In addition, the developed pattern was heated (hard baked) at 110 to 180 ° C. without washing with the cleaning liquid composition, thereby (i) a 1: 1 contact hole pattern having a film thickness of 140 nm and a hole diameter of 100 nm (Comparative Example 2). Or (ii) a 1: 1 contact hole pattern (Comparative Example 4) having a film thickness of 60 nm and a hole diameter of 30 nm. The hole aperture size of the pattern was measured using an electron microscope (Critical Dimension Scanning Electron Microscope: CD-SEM, manufacturer: Hitachi, device name: S9220).

(d) 상기 (c)와 동일하게 포토레지스트 패턴을 현상하거나(PTD 공정 사용), 소정의 브라이트 필드(bright field) 포토마스크(예를 들면, 100nm 1:1 폴(pole) 패턴을 갖는 포토마스크)를 사용하여 노광하고, PEB 공정 후, nBA(n-부틸 아세테이트) 유기 용매로 30초간 현상함으로써 포토레지스트 패턴(100nm 1:1 콘택트 홀 패턴)을 현상한 다음(NTD 공정 사용), 순수로 30초 동안 세정하고, 상기 A 단계에서 제조한 세정액 조성물을 현상된 포토레지스트 패턴 표면에 뿌리고 15초 동안 접촉시킨 다음, 스핀 드라이를 통해서 웨이퍼를 건조한 후, 110 내지 180℃에서 가열(하드 베이크)하여 (i) 필름 두께 140nm, 홀 구경 100nm 의 1 : 1 콘택트 홀(Contact Hole) 패턴의 홀 크기를 수축시키거나(실시예 1 내지 22(PTD 공정), 실시예 23 내지 24(NTD 공정)), (ii) 필름 두께 60nm, 홀 구경 30nm 의 1 : 1 콘택트 홀(Contact Hole) 패턴의 홀 크기를 수축시켰다(실시예 25 내지 26(PTD 공정)). 상기 (c)와 동일한 방법으로 패턴의 홀 구경 크기를 측정하여 그 결과를 하기 표 1 내지 3에 나타내었다.
(d) developing a photoresist pattern in the same manner as in (c) (using a PDT process), or a photomask having a predetermined bright field photomask (eg, a 100 nm 1: 1 pole pattern). ), And after the PEB process, the photoresist pattern (100 nm 1: 1 contact hole pattern) was developed by using nBA (n-butyl acetate) organic solvent for 30 seconds (using NTD process), followed by pure water 30 After cleaning for seconds, the cleaning liquid composition prepared in step A was sprayed on the surface of the developed photoresist pattern and contacted for 15 seconds, and the wafer was dried by spin drying, and then heated (hard baked) at 110 to 180 ° C. ( i) shrinking the hole size of the 1: 1 contact hole pattern having a film thickness of 140 nm and a hole diameter of 100 nm (Examples 1 to 22 (PTD process), Examples 23 to 24 (NTD process)), ( ii) 1: 1 contact holes with a film thickness of 60 nm and hole diameter of 30 nm (C ontact Hole) pattern to shrink the hole size (Examples 25 to 26 (PTD process)). The hole aperture size of the pattern was measured in the same manner as in (c), and the results are shown in Tables 1 to 3 below.

　 이온성 화합물Ionic compounds 용매menstruum 하드 베이크 온도(℃)Hard bake temperature (℃) 홀 구경 크기(nm)Hole Aperture Size (nm) 화학식Chemical formula 함량(ppm)Content (ppm) 비교예 1Comparative Example 1 -- -- -- xx 100 100 비교예 2Comparative Example 2 -- -- -- 150150 100 100 실시예 1Example 1 1a1a 1000 1000 순수물Pure water 130130 82 82 실시예 2Example 2 1b1b 1000 1000 순수물Pure water 130130 80 80 실시예 3Example 3 1c1c 1000 1000 순수물Pure water 130130 80 80 실시예 4Example 4 1d1d 100 100 순수물Pure water 130130 92 92 실시예 5Example 5 1d1d 500 500 순수물Pure water 130130 80 80 실시예 6Example 6 1d1d 1000 1000 순수물Pure water 130130 78 78 실시예 7Example 7 1d1d 3000 3000 순수물Pure water 130130 75 75 실시예 8Example 8 1d1d 1000 1000 순수물Pure water 140140 71 71 실시예 9Example 9 1d1d 1000 1000 순수물Pure water 150150 62 62 실시예 10Example 10 1f1f 1000 1000 순수물Pure water 130130 81 81

　 이온성 화합물Ionic compounds 용매menstruum 하드 베이크 온도(℃)Hard bake temperature (℃) 홀 구경 크기(nm)Hole Aperture Size (nm) 화학식Chemical formula 함량(ppm)Content (ppm) 실시예 11Example 11 1g1 g 1000 1000 순수물Pure water 130130 80 80 실시예 12Example 12 2a2a 1000 1000 순수물Pure water 130130 81 81 실시예 13Example 13 2c2c 1000 1000 순수물Pure water 130130 80 80 실시예 14Example 14 2d2d 1000 1000 순수물Pure water 130130 79 79 실시예 15Example 15 2e2e 100 100 순수물Pure water 130130 90 90 실시예 16Example 16 2e2e 500 500 순수물Pure water 130130 88 88 실시예 17Example 17 2e2e 1000 1000 순수물Pure water 130130 75 75 실시예 18Example 18 2e2e 3000 3000 순수물Pure water 130130 80 80 실시예 19Example 19 2e2e 1000 1000 순수물Pure water 140140 73 73 실시예 20Example 20 2e2e 1000 1000 순수물Pure water 150150 65 65 실시예 21Example 21 2f2f 1000 1000 순수물Pure water 130130 81 81 실시예 22Example 22 2g2 g 1000 1000 순수물Pure water 130130 82 82 실시예 23Example 23 1d1d 1000 1000 헥산올Hexanol 130130 68 68 실시예 24Example 24 2e2e 1000 1000 헥산올Hexanol 130130 65 65

　 이온성 화합물Ionic compounds 용매menstruum 하드 베이크 온도(℃)Hard bake temperature (℃) 홀 구경 크기(nm)Hole Aperture Size (nm) 화학식Chemical formula 함량(ppm)Content (ppm) 비교예 3Comparative Example 3 -- -- -- xx 3030 비교예 4Comparative Example 4 -- -- -- 150150 3030 실시예 25Example 25 1d1d 1000 1000 순수물Pure water 130130 2222 실시예 26Example 26 2e2e 1000 1000 순수물Pure water 130130 2323

상기 결과로부터, 본 발명에 따른 이온성 화합물이 포함되어 있는 세정액 조성물(린스액)로 패턴을 세정 및 세정 후 가열(하드 베이크)할 경우, PTD, NTD 공정에 관계없이 패턴의 홀 크기를 효과적으로 감소시킬 수 있음을 알 수 있다. 또한, 통상적으로, 높은 유리전이온도(Tg)를 갖는 포토레지스트 조성물(감광성 고분자)은 낮은 하드 베이크 온도(150℃ 이하)에서는 콘택트 홀(C/H) 패턴의 홀 크기를 감소(shrink)시키지 못하지만, 본원발명의 세정액 조성물을 사용할 경우, 조성물의 이온성 화합물들이 포토레지스트 패턴 표면에 흡착되고, 포토레지스트 조성물의 유리전이온도(Tg)를 감소시키는 효과를 일으킴으로써, 낮은 하드 베이크 온도(150℃ 이하)에서도 쉽게 콘택트 홀(C/H) 패턴의 홀 크기를 감소(shrink)시킬 수 있음을 알 수 있다. 또한, 상기 결과로부터, 하드 베이크 온도 조절 및 이온성 화합물의 종류 및 양을 조절함으로써, C/H 패턴 감소 정도를 조절할 수 있음을 알 수 있다.From the above results, when the pattern is washed with the cleaning liquid composition (rinse liquid) containing the ionic compound according to the present invention and heated (hard bake), the hole size of the pattern is effectively reduced regardless of the PTD and NTD processes. It can be seen that. Also, photoresist compositions (photosensitive polymers) with high glass transition temperatures (Tg) typically do not shrink the hole size of the contact hole (C / H) pattern at low hard bake temperatures (150 ° C. or less). When the cleaning liquid composition of the present invention is used, the ionic compounds of the composition are adsorbed on the surface of the photoresist pattern and have an effect of reducing the glass transition temperature (Tg) of the photoresist composition, thereby lowering the hard bake temperature (150 ° C. or less). It can be seen that also can easily shrink the hole size of the contact hole (C / H) pattern. In addition, it can be seen from the above results that the degree of C / H pattern reduction can be controlled by controlling the hard bake temperature and adjusting the type and amount of the ionic compound.

Claims (6)

하기 화학식 1로 표시되는 화합물, 하기 화학식 2로 표시되는 화합물 및 이들의 혼합물로 이루어진 군으로부터 선택되는 이온성 화합물; 및
용매를 포함하는 포토리소그래피용 세정액 조성물.
[화학식 1]
Figure pat00021

[화학식 2]
Figure pat00022

상기 화학식 1 및 2에서, R1 및 R2는 각각 독립적으로 수소 원자(H), 또는 치환 또는 비치환된 탄소수 1 내지 25의 탄화수소기이다.An ionic compound selected from the group consisting of a compound represented by Formula 1, a compound represented by Formula 2, and a mixture thereof; And
Cleaning liquid composition for photolithography containing a solvent.
[Formula 1]
Figure pat00021

(2)
Figure pat00022

In Formulas 1 and 2, R 1 and R 2 are each independently a hydrogen atom (H) or a substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms. 제1항에 있어서, 상기 화학식 1로 표시되는 이온성 화합물은 하기 화학식 1a 내지 1g로 표시되는 이온성 화합물로 이루어진 군으로부터 선택되는 것이고, 상기 화학식 2로 표시되는 이온성 화합물은 하기 화학식 2a 내지 2i로 표시되는 이온성 화합물로 이루어진 군으로부터 선택되는 것인 포토리소그래피용 세정액 조성물.
[화학식 1a]
Figure pat00023

[화학식 1b]
Figure pat00024

[화학식 1c]
Figure pat00025

[화학식 1d]
Figure pat00026

[화학식 1e]
Figure pat00027

[화학식 1f]
Figure pat00028

[화학식 1g]
Figure pat00029

[화학식 2a]
Figure pat00030

[화학식 2b]
Figure pat00031

[화학식 2c]
Figure pat00032

[화학식 2d]
Figure pat00033

[화학식 2e]
Figure pat00034

[화학식 2f]

[화학식 2g]
Figure pat00036

[화학식 2h]
Figure pat00037

[화학식 2i]
Figure pat00038
The ionic compound represented by Formula 1 is selected from the group consisting of ionic compounds represented by Formulas 1a to 1g, and the ionic compound represented by Formula 2 is represented by Formulas 2a to 2i. Cleaning liquid composition for photolithography is selected from the group consisting of ionic compounds represented by.
[Formula 1a]
Figure pat00023

[Chemical Formula 1b]
Figure pat00024

[Chemical Formula 1c]
Figure pat00025

≪ RTI ID = 0.0 &
Figure pat00026

[Formula 1e]
Figure pat00027

(1f)
Figure pat00028

[Formula 1g]
Figure pat00029

(2a)
Figure pat00030

(2b)
Figure pat00031

[Formula 2c]
Figure pat00032

(2d)
Figure pat00033

[Formula 2e]
Figure pat00034

(2f)

[Formula 2g]
Figure pat00036

[Formula 2h]
Figure pat00037

[Formula 2i]
Figure pat00038
 제1항에 있어서, 전체 포토리소그래피용 세정액 조성물에 대하여, 상기 이온성 화합물의 함량은 0.001 내지 5중량%이고, 나머지는 용매인 것인 포토리소그래피용 세정액 조성물.The cleaning liquid composition for photolithography according to claim 1, wherein the content of the ionic compound is 0.001 to 5% by weight, and the remainder is a solvent, based on the total cleaning liquid composition for photolithography. 제1항에 있어서, 상기 용매는, 물(순수), 유기 용매, 또는 물과 유기 용매를 혼합한 혼합 용매인 것인 포토리소그래피용 세정액 조성물.The cleaning liquid composition for photolithography according to claim 1, wherein the solvent is water (pure), an organic solvent, or a mixed solvent in which water and an organic solvent are mixed. 제1항에 있어서, 상기 용매는, 포지티브 톤 현상(positive tone development: PTD) 공정 사용 시, 물, 1가(價) 또는 다가(多價) 알코올계 유기 용매 및 이들의 혼합물로 이루어진 군에서 선택되는 것이고, 네가티브 톤 현상(negative tone development: NTD) 공정 사용 시, 지용성 알코올 용매인 것인 포토리소그래피용 세정액 조성물.The method of claim 1, wherein the solvent is selected from the group consisting of water, a monohydric or polyhydric alcohol-based organic solvent, and mixtures thereof when using a positive tone development (PTD) process. The cleaning liquid composition for photolithography which is a fat-soluble alcohol solvent at the time of using a negative tone development (NTD) process. 피식각층이 형성된 반도체 기판 상에 포토레지스트막을 형성하는 단계;
상기 포토레지스트막을 노광 및 현상하여 포토레지스트 패턴(콘택트 홀 패턴)을 형성하는 단계;
상기 포토레지스트 패턴을 청구항 1 내지 5에 따른 포토리소그래피용 세정액 조성물로 세정하는 단계; 및
상기 세정된 포토레지스트 패턴을 건조하고, 110 내지 180℃로 가열(하드 베이크)하여, 패턴의 홀 크기를 수축시키는 단계를 포함하는 포토레지스트 미세패턴 형성방법.Forming a photoresist film on the semiconductor substrate on which the etched layer is formed;
Exposing and developing the photoresist film to form a photoresist pattern (contact hole pattern);
Washing the photoresist pattern with the cleaning liquid composition for photolithography according to claims 1 to 5; And
Drying the cleaned photoresist pattern and heating (hard bake) to 110 to 180 ° C. to shrink the hole size of the pattern.
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KR20070086817A (en) * 2004-12-09 2007-08-27 토쿄오오카코교 가부시기가이샤 Cleaning liquid for lithography and method for resist pattern formation
US20090007936A1 (en) * 2005-11-09 2009-01-08 Stephan Uhl Composition with Surface Modifying Properties
KR20090069875A (en) * 2007-12-26 2009-07-01 주식회사 동진쎄미켐 Salt for controlling acid-diffusion and photoresist composition including the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070086817A (en) * 2004-12-09 2007-08-27 토쿄오오카코교 가부시기가이샤 Cleaning liquid for lithography and method for resist pattern formation
JP4459857B2 (en) * 2004-12-09 2010-04-28 東京応化工業株式会社 Lithographic cleaning liquid and resist pattern forming method using the same
US20090007936A1 (en) * 2005-11-09 2009-01-08 Stephan Uhl Composition with Surface Modifying Properties
KR20090069875A (en) * 2007-12-26 2009-07-01 주식회사 동진쎄미켐 Salt for controlling acid-diffusion and photoresist composition including the same

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