KR101863636B1 - 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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KR101863636B1
KR101863636B1 KR1020110054873A KR20110054873A KR101863636B1 KR 101863636 B1 KR101863636 B1 KR 101863636B1 KR 1020110054873 A KR1020110054873 A KR 1020110054873A KR 20110054873 A KR20110054873 A KR 20110054873A KR 101863636 B1 KR101863636 B1 KR 101863636B1
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pattern
solvent
liquid composition
cleaning liquid
photolithography
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KR20120135958A (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)
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  • Oil, Petroleum & Natural Gas (AREA)
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  • Health & Medical Sciences (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

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 형성방법이 개시된다. 상기 포토리소그래피용 세정액 조성물은 하기 화학식 1로 표시되는 화합물, 하기 화학식 2로 표시되는 화합물 및 이들의 혼합물로 이루어진 군으로부터 선택되는 이온성 화합물; 및 용매를 포함한다.
[화학식 1]

Figure 112011042822936-pat00039

[화학식 2]
Figure 112011042822936-pat00040

상기 화학식 1 및 2에서, R1 및 R2는 각각 독립적으로 수소 원자(H), 또는 치환 또는 비치환된 탄소수 1 내지 25의 탄화수소기이다.A cleaning liquid composition for photolithography capable of reducing the size of a contact hole pattern by pattern cleaning and heating after cleaning in a contact hole pattern forming process and a method for forming a photoresist fine pattern using the same. Wherein the cleaning liquid composition for photolithography comprises 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 a mixture thereof; And a solvent.
[Chemical Formula 1]
Figure 112011042822936-pat00039

(2)
Figure 112011042822936-pat00040

In the general 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.

Description

포토리소그래피용 세정액 조성물 및 이를 이용한 포토레지스트 미세패턴 형성방법{Cleaning composition for photolithography and method for forming photoresist fine pattern using the same}A cleaning liquid composition for photolithography and a method for forming a 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, to a cleaning liquid composition for photolithography capable of reducing the size of a contact hole pattern by pattern cleaning and heating after cleaning in a contact hole pattern forming process, And 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 for manufacturing semiconductor devices have also been improved to cope with such miniaturization and integration. In addition, extreme ultraviolet lithography (EUVL) technology with a wavelength of 13.4 nm is used to realize a fine pattern according to the degree of semiconductor integration. As the wavelength of the exposure source becomes smaller, the size of the limiting resolution gradually decreases. However, there are many technological difficulties to reach the pattern size to be ultimately attained.

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.
Particularly, there is a great difficulty in resolving a contact hole pattern in a dark filed area where light information of an exposure light source is small. In order to overcome this problem, various pattern shrink techniques have been developed.

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.
Korean Patent Laid-Open Nos. 10-2009-0082232, 10-2010-0047229, 10-2010-0014642, and 10-2008-0014388 disclose a new coating film on a pattern-completed substrate And a method of chemically shrinking the contact hole pattern, that is, reducing the hole size, is disclosed. However, these methods have disadvantages in that they are disadvantageous in terms of productivity and cost because additional processes are added to the coating film.

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 provide a method of reducing the hole size of a contact hole pattern by pattern cleaning and heating after cleaning A cleaning liquid composition for photolithography, and a method for 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 provides 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 a cleaning solvent composition for photolithography comprising a solvent.

[화학식 1] [Chemical Formula 1]

Figure 112011042822936-pat00001
Figure 112011042822936-pat00001

[화학식 2] (2)

Figure 112011042822936-pat00002
Figure 112011042822936-pat00002

상기 화학식 1 및 2에서, R1 및 R2는 각각 독립적으로 수소 원자(H), 또는 치환 또는 비치환된 탄소수 1 내지 25의 탄화수소기이다.
In the general 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 of manufacturing a semiconductor device, comprising: forming a photoresist film on a semiconductor substrate on which an etching layer is formed; Exposing and developing the photoresist film to form a photoresist pattern (contact hole pattern); Cleaning the photoresist pattern with the cleaning liquid composition for photolithography; And drying the washed photoresist pattern and heating (hard baking) the resultant at 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 a hole size of a photoresist pattern (contact hole pattern) through pattern cleaning and heating (110 to 180 ° C) after cleaning. And is useful for fine pattern formation.

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 comprises 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 a solvent.

Figure 112011042822936-pat00003
Figure 112011042822936-pat00003

Figure 112011042822936-pat00004
Figure 112011042822936-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.
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 oxygen atom (O), nitrogen atom (N) (E.g., an alkyl group, a hydroxyalkyl group, a benzyl alcohol group, an imidazole group, etc.) which is unsubstituted or substituted with a hetero atom such as a sulfur atom (S) , A nonyl group, a decyl group, a lauryl group, a pentadecyl group, a myristyl group, a palmityl group, and a stearyl group.

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 a photoresist pattern during cleaning and may serve as a polymer plasticizer in the course of heating (hard bake) to lower the glass transition temperature (Tg) of the photoresist composition (photosensitive polymer) As the ionic compound having the formula (1) and / or the formula (2), there may be used. The content of the ionic compound is 0.001 to 5 wt%, preferably 0.005 to 1 wt%, more preferably 0.01 to 0.5 wt%, and most preferably 0.05 to 0.1 wt%, based on the entire photolithography cleaning liquid composition %to be. If the content of the ionic compound is less than 0.001% by weight, it may not exhibit a pattern shrinking function, and if it exceeds 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 the above formula (1) include ionic compounds represented by the following formulas (1a) to (1g).

[화학식 1a][Formula 1a]

Figure 112011042822936-pat00005
Figure 112011042822936-pat00005

[화학식 1b][Chemical Formula 1b]

Figure 112011042822936-pat00006
Figure 112011042822936-pat00006

[화학식 1c][Chemical Formula 1c]

Figure 112011042822936-pat00007
Figure 112011042822936-pat00007

[화학식 1d]≪ RTI ID = 0.0 &

Figure 112011042822936-pat00008
Figure 112011042822936-pat00008

[화학식 1e][Formula 1e]

Figure 112011042822936-pat00009
Figure 112011042822936-pat00009

[화학식 1f](1f)

Figure 112011042822936-pat00010
Figure 112011042822936-pat00010

[화학식 1g][Formula 1g]

Figure 112011042822936-pat00011

Figure 112011042822936-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 the formula (2) include ionic compounds represented by the following formulas (2a) to (2i).

[화학식 2a](2a)

Figure 112011042822936-pat00012
Figure 112011042822936-pat00012

[화학식 2b](2b)

Figure 112011042822936-pat00013
Figure 112011042822936-pat00013

[화학식 2c][Chemical Formula 2c]

Figure 112011042822936-pat00014
Figure 112011042822936-pat00014

[화학식 2d](2d)

Figure 112011042822936-pat00015
Figure 112011042822936-pat00015

[화학식 2e][Formula 2e]

Figure 112011042822936-pat00016
Figure 112011042822936-pat00016

[화학식 2f](2f)

Figure 112011042822936-pat00017
Figure 112011042822936-pat00017

[화학식 2g][Chemical Formula 2g]

Figure 112011042822936-pat00018
Figure 112011042822936-pat00018

[화학식 2h][Chemical Formula 2h]

Figure 112011042822936-pat00019
Figure 112011042822936-pat00019

[화학식 2i](2i)

Figure 112011042822936-pat00020

Figure 112011042822936-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 to be used in the present invention may be water (pure water), an organic solvent, or a mixed solvent in which water and an organic solvent are mixed. For example, when using a positive tone development (PTD) process, the solvent may be water, a monovalent or multivalent alcohol organic solvent, or a mixed solvent thereof. 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, Or an esterified product thereof. In addition, when the negative tone development (NTD) process is used, a solvent such as a liposoluble alcohol solvent (such as butanol, hexanol, heptanol, and octanol) may be used 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 same as that of the cleaning liquid composition for photolithography except for the ionic compound. When a mixed solvent is used in the PTD process, the content of the alcoholic organic solvent is preferably 0.01 To 50% by weight, preferably 0.1 to 20% by weight. If the content of the water-soluble alcoholic organic solvent exceeds 50 wt% with respect to the total mixed solvent, the photoresist pattern may dissolve in the solvent to cause a pattern distortion phenomenon.

본 발명에 따른 포토리소그래피용 세정액 조성물은, 필요에 따라, 계면활성제 등의 첨가물을 더욱 포함할 수 있다.The cleaning liquid composition for photolithography according to the present invention may further contain an additive such as a surfactant if necessary.

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 0.005 to 1 part by weight per 100 parts by weight of the cleaning liquid composition for photolithography 0.01 to 0.5 parts by weight, and most preferably 0.01 to 0.1 parts by weight of a 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 a cleaning process of a conventional photolithography process and can form a fine pattern by shrinking the hole size of a photoresist pattern (contact hole pattern) formed through a heating process after pattern cleaning have. For example, a method of forming a photoresist fine pattern according to the present invention includes the steps of: (a) forming a photoresist film on a semiconductor substrate on which a semiconductor layer is formed; (b) exposing and developing the photoresist film to form a photoresist pattern (C) cleaning the photoresist pattern with the cleaning liquid composition for photolithography; and (d) spin-spinning (spin-drying) the cleaned photoresist pattern. ) And the like, 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 method of forming the photoresist fine pattern, conventional photoresist compositions (for example, photoresist compositions of the following examples and comparative examples) can be used as the photoresist film and the photoresist composition for pattern formation without limitation, The cleaning of the photoresist pattern may be performed by the secondary cleaning with the cleaning composition of the present invention after the primary cleaning using pure water. If the heating temperature is less than 110 ° C during the heating (hard bake) process, The size may not be effectively shrunk. If the heating temperature exceeds 180 DEG C, the pattern may be distorted by 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 Solution 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 compositions shown in Tables 1 to 3, commercialized ionic compounds having the respective chemical formulas (Aldrich, manufactured by TCI) and a solvent were mixed for 4 hours to completely dissolve the ionic compound in a solvent, Sized pores 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 Solution 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 the formation of a photoresist pattern and the evaluation of a cleaning liquid composition, a photosensitive polymer was synthesized as follows. 117.2 g (0.5 mol) of 2-methyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate (0.1 mol) of 2-oxotetrahydrofuran-3-yl methacrylate, 68.0 g (0.4 mol) of 2-oxotetrahydrofuran-3-yl methacrylate, and azobis (isobutyronitrile) Was dissolved in 125 g of anhydrous tetrahydrofuran (THF), the gas was removed using an ampoule by the freezing method, and the reaction product was polymerized at 68 DEG C for 24 hours. After the polymerization is completed, the reaction solution is slowly dropped to an excess amount of diethyl ether to precipitate the precipitate. The precipitate is dissolved again in tetrahydrofuran (THF) and then re-precipitated in diethyl ether to prepare a photopolymerized photosensitive polymer (terpolymer) (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, 10 parts by weight of diphenyl para-toluenesulfonylnonium plate (TPS-NF), a base stabilizer (manufactured by Nippon Denshoku Kogyo Co., Ltd.) as a photo- 20 parts by weight of triethanolamine was added to propylene glycol monomethyl ether acetate (PGMEA) in 100 parts by weight of the photoacid generator, and the mixture was stirred for 12 hours or longer to completely dissolve the nylon material filter. And then sequentially filtered through a polytetrafluoroethylene (PTFE) material filter to prepare a photoresist composition.

(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) The photoresist composition prepared in (b) above was spin-coated on the top of the etching layer of a silicon wafer to form a photoresist thin film (film), followed by heating (prebaking) (I) exposure with an ArF ASML 1200B instrument with a numerical aperture (NA) of 0.85 (Examples 1 to 24, Comparative Examples 1 to 4), and (ii) exposure using a predetermined (dark field) photomask 2), (ii) Exposure with an extreme ultraviolet lithography (EUVL) exposure machine (Examples 25 to 26 and Comparative Examples 3 to 4), followed by post exposure bake (PEB) at 125 ° C for 60 seconds . The wafer thus baked (heated) was developed for 30 seconds in an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide (TMAH) (using the PTD process) to obtain a (i) 1: 1 contact hole with a film thickness of 140 nm and a hole diameter of 100 nm Contact Hole pattern (Comparative Example 1) or (ii) 1: 1 contact hole pattern (Comparative Example 3) having a film thickness of 60 nm and a hole diameter of 30 nm was formed. Further, the developed pattern was heated (hard baked) at 110 to 180 ° C without washing with the cleaning liquid composition to obtain 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 diameter of the pattern was measured using an electron microscope (Critical Dimension Scanning Electron Microscope: CD-SEM, manufactured by Hitachi, Ltd., 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) a photoresist pattern is developed (using a PTD process) or a predetermined bright field photomask (for example, a photomask having a 100 nm 1: 1 pole pattern) (100 nm 1: 1 contact hole pattern) was developed by using an nBE (n-butyl acetate) organic solvent for 30 seconds and then developed (using an NTD process) And the cleaning liquid composition prepared in the above step A is sprinkled on the surface of the developed photoresist pattern and contacted for 15 seconds. Thereafter, the wafer is dried by spin-drying and then heated (hard baked) at 110 to 180 ° C i) shrink the hole size of a 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) A 1: 1 contact hole (C) having a film thickness of 60 nm and a hole diameter of 30 nm ontact Hole patterns (Examples 25-26 (PTD process)). The hole diameter of the pattern was measured in the same manner as in (c) above, and the results are shown in Tables 1 to 3 below.

　 이온성 화합물Ionic compound 용매menstruum 하드 베이크 온도(℃)Hard bake temperature (℃) 홀 구경 크기(nm)Hole size (nm) 화학식The 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 compound 용매menstruum 하드 베이크 온도(℃)Hard bake temperature (℃) 홀 구경 크기(nm)Hole size (nm) 화학식The 함량(ppm)Content (ppm) 실시예 11Example 11 1g1g 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 2g2g 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 compound 용매menstruum 하드 베이크 온도(℃)Hard bake temperature (℃) 홀 구경 크기(nm)Hole size (nm) 화학식The 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, it can be seen that when the pattern is cleaned, cleaned and heated (hard bake) with the cleaning liquid composition (rinse solution) containing the ionic compound according to the present invention, the hole size of the pattern is effectively reduced . In addition, photoresist compositions (photosensitive polymers) having a high glass transition temperature (Tg) typically do not shrink the hole size of the contact hole (C / H) pattern at low hard bake temperatures , 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 the effect of decreasing the glass transition temperature (Tg) of the photoresist composition, whereby a low hard bake temperature ), It is easy to shrink the hole size of the contact hole (C / H) pattern. From the above results, it can be seen that the degree of C / H pattern reduction can be controlled by controlling the hard bake temperature and the kind and amount of the ionic compound.

Claims (6)

하기 화학식 2로 표시되는 이온성 화합물; 및
용매를 포함하는 포토리소그래피용 세정액 조성물.
[화학식 2]
Figure 112017110218847-pat00022

상기 화학식 2에서, R2는 수소 원자(H), 또는 치환 또는 비치환된 탄소수 1 내지 25의 탄화수소기이다.An ionic compound represented by the following formula (2); And
A cleaning liquid composition for photolithography comprising a solvent.
(2)
Figure 112017110218847-pat00022

In Formula 2, R 2 is a hydrogen atom (H), or a substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms. 제1항에 있어서, 상기 화학식 2로 표시되는 이온성 화합물은 하기 화학식 2a 내지 2i로 표시되는 이온성 화합물로 이루어진 군으로부터 선택되는 것인 포토리소그래피용 세정액 조성물.
[화학식 2a]
Figure 112017110218847-pat00030

[화학식 2b]
Figure 112017110218847-pat00031

[화학식 2c]
Figure 112017110218847-pat00032

[화학식 2d]
Figure 112017110218847-pat00033

[화학식 2e]
Figure 112017110218847-pat00034

[화학식 2f]
Figure 112017110218847-pat00035

[화학식 2g]
Figure 112017110218847-pat00036

[화학식 2h]
Figure 112017110218847-pat00037

[화학식 2i]
Figure 112017110218847-pat00038
2. The cleaning liquid composition for photolithography according to claim 1, wherein the ionic compound represented by the general formula (2) is selected from the group consisting of ionic compounds represented by the following general formulas (2a) to (2i).
(2a)
Figure 112017110218847-pat00030

(2b)
Figure 112017110218847-pat00031

[Chemical Formula 2c]
Figure 112017110218847-pat00032

(2d)
Figure 112017110218847-pat00033

[Formula 2e]
Figure 112017110218847-pat00034

(2f)
Figure 112017110218847-pat00035

[Chemical Formula 2g]
Figure 112017110218847-pat00036

[Chemical Formula 2h]
Figure 112017110218847-pat00037

(2i)
Figure 112017110218847-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 in the cleaning liquid composition for the entire photolithography is 0.001 to 5% by weight, and the balance is a solvent. 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 water), 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 monovalent or multivalent alcohol organic solvent, and mixtures thereof when using a positive tone development (PTD) process. And is a lipid-soluble alcohol solvent when used in 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 5의 어느 한 항에 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 etching layer is formed;
Exposing and developing the photoresist film to form a photoresist pattern (contact hole pattern);
Cleaning the photoresist pattern with the cleaning liquid composition for photolithography according to any one of claims 1 to 5; And
Drying the cleaned photoresist pattern, and heating (hard baking) the resultant at 110 to 180 DEG C to shrink the hole size of the pattern.
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