KR20120066227A - Cleaning composition for photolithography - Google Patents

Cleaning composition for photolithography Download PDF

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KR20120066227A
KR20120066227A KR1020100127467A KR20100127467A KR20120066227A KR 20120066227 A KR20120066227 A KR 20120066227A KR 1020100127467 A KR1020100127467 A KR 1020100127467A KR 20100127467 A KR20100127467 A KR 20100127467A KR 20120066227 A KR20120066227 A KR 20120066227A
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South Korea
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group
formula
water
soluble polymer
carbon atoms
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KR1020100127467A
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Korean (ko)
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오승근
이재우
이정열
김정식
김재현
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주식회사 동진쎄미켐
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Priority to KR1020100127467A priority Critical patent/KR20120066227A/en
Priority to PCT/KR2011/009526 priority patent/WO2012081865A2/en
Publication of KR20120066227A publication Critical patent/KR20120066227A/en

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    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • 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
    • G03F7/42—Stripping or agents therefor
    • 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
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • 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
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • 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
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Detergent Compositions (AREA)

Abstract

PURPOSE: A cleaning composition is provided to prevent pattern collapse and resist scum generated at photo resist pattern formation, and to restrain the increase of line width roughness. CONSTITUTION: A cleaning composition comprises a water-soluble polymer comprising a repeating unit in chemical formula 1, a surfactant, and a solvent. In chemical formula 1, R1 is hydrogen, fluorine, a methyl group, C1-20 fluorinated alkyl group or C1-5 hydroxyalkyl group. R2 is not exist, or C1-20 alkyl group. The content of the water soluble polymer is 0.001-5 weight% based on the total cleaning composition, the content of the surfactant is 0.001-5 weight% based on the total cleaning composition, and a residual component is solvent.

Description

포토리소그래피용 세정액 조성물{Cleaning composition for photolithography}Cleaning composition for photolithography

본 발명은 세정액 조성물에 관한 것으로서, 더욱 상세하게는, 포토레지스트 패턴 형성 시 발생하는 레지스트 스컴(scum) 및 패턴 쓰러짐을 방지하고, 선폭 거칠기(line width roughness: LWR)의 수치 증대를 억제(개선)할 수 있는 포토리소그래피용 세정액 조성물에 관한 것이다.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning liquid composition, and more particularly, to prevent resist scum and pattern collapse that occur when forming a photoresist pattern, and to suppress an increase in the numerical value of line width roughness (LWR) (improvement). It relates to a cleaning liquid composition for photolithography that can be made.

반도체 디바이스가 소형화 및 집적화됨에 따라, 반도체 디바이스의 제조에 사용되는 포토레지스트 조성물(레지스트 재료)도 고해상도의 패턴을 얻을 수 있도록 개량되어 왔다. 그러나, 소형화 및 집적화에 따른 고해상력의 패터닝이 요구될수록, 포토레지스트 조성물을 사용한 미세 패턴 구현 시 여러 가지 문제점들이 발생되었으며, 예를 들면, 레지스트 패턴 불량, 레지스트 스컴(scum), 선폭 거칠기(line width roughness: LWR)의 수치 증대, 패턴 쓰러짐 등의 결함(defect)들로 인한 반도체 디바이스의 수율 저하가 발생되었다.
As semiconductor devices are downsized and integrated, photoresist compositions (resist materials) used in the manufacture of semiconductor devices have also been improved to obtain high resolution patterns. However, as the patterning of high resolution due to miniaturization and integration has been required, various problems have arisen in implementing a fine pattern using a photoresist composition, for example, a resist pattern defect, a resist scum, and a line width roughness. Roughness: The decrease in yield of the semiconductor device occurred due to defects such as numerical increase of LWR) and pattern collapse.

30nm 이하 패턴 해상력의 반도체 디바이스를 생산하기 위해서, 노광원의 파장이 13.4nm인 극자외선 리소그라피(extreme ultraviolet lithography: EUVL) 기술이 이용되고 있으며, 상기 기술을 사용하기 위해서는 앞서 언급했던 결함들로 인한 문제점을 극복해야 한다. 레지스트 스컴(scum), 선폭 거칠기(LWR)의 수치 증대, 패턴 쓰러짐 등의 현상은 포토레지스트 조성물의 성능 저하에 의해 발생되는 것이 대부분이지만, 세정 기술을 통해서 상기 결함들을 극복할 수 있다. 예를 들면, 일반적으로 공정 진행 시 순수(세정액)를 사용하여 세정을 진행하고 있으나, 계면활성제를 상기 세정액에 첨가하여 세정액의 표면장력을 줄이면, 스핀 아웃을 통한 웨이퍼 건조 시 발생하는 패턴 쓰러짐을 방지할 수 있다. 그러나, 상기 계면활성제를 포함하는 세정액은 레지스트 스컴(scum) 제거, 선폭 거칠기(LWR)의 수치 증대 개선(억제) 등을 효과적으로 수행할 수 없다.
In order to produce a semiconductor device having a pattern resolution of 30 nm or less, extreme ultraviolet lithography (EUVL) technology having a wavelength of 13.4 nm of an exposure source is used, and the problems caused by the above-mentioned defects are used to use the above technology. Overcome it. Phenomenon such as increase in resist scum, line width roughness (LWR), pattern collapse, etc. is mostly caused by deterioration of the photoresist composition. However, the above-described defects can be overcome by a cleaning technique. For example, in general, cleaning is performed using pure water (cleaning liquid) during the process. However, when surfactant is added to the cleaning liquid to reduce the surface tension of the cleaning liquid, the pattern falling during wafer drying through spin out is prevented. can do. However, the cleaning liquid containing the surfactant may not effectively perform resist scum removal and increase (suppression) of line width roughness LWR.

따라서, 본 발명의 목적은, 레지스트 스컴(scum) 및 패턴 쓰러짐을 방지하고, 선폭 거칠기(LWR)의 수치 증대를 억제(개선)할 수 있는 세정액 조성물을 제공하는 것이다.
Accordingly, an object of the present invention is to provide a cleaning liquid composition which can prevent resist scum and pattern collapse and can suppress (improve) increase in numerical value of line width roughness LWR.

상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 반복단위를 포함하는 수용성 고분자; 계면활성제; 및 용매를 포함하는 세정액 조성물을 제공한다.In order to achieve the above object, the present invention is a water-soluble polymer comprising a repeating unit represented by the formula (1); Surfactants; And it provides a cleaning liquid composition comprising a solvent.

[화학식 1] [Formula 1]

Figure pat00001
Figure pat00001

상기 화학식 1에서, R1은 수소 원자(H), 불소 원자(F), 메틸기(-CH3), 탄소수 1 내지 20의 불소화 알킬기 또는 탄소수 1 내지 5의 히드록시알킬기이고, R2는 존재하지 않거나, 탄소수 1 내지 20의 알킬기이다.
In Formula 1, R 1 is a hydrogen atom (H), a fluorine atom (F), a methyl group (-CH 3 ), a fluorinated alkyl group of 1 to 20 carbon atoms or a hydroxyalkyl group of 1 to 5 carbon atoms, R 2 is not present Or an alkyl group having 1 to 20 carbon atoms.

본 발명에 따른 세정액 조성물은, 포토레지스트 패턴 형성 시 문제가 되는, 용해되어야 할 포토레지스트 조성물 중 부분적으로 용해되지 않은 부분(레지스트 스컴(scum))이나, 패턴의 거친 부분(선폭 거칠기(line width roughness: LWR)의 수치가 증대된 부분)을 상기 수용성 고분자에 흡착시키고 물 등의 용매에 용해시킴으로써 제거할 수 있다. 또한, 계면활성제를 통하여 패턴 쓰러짐을 방지할 수 있다. 따라서, 본 발명의 세정액 조성물은 극자외선 리소그라피(extreme ultraviolet lithography: EUVL) 기술을 사용한 미세 패턴 형성에 유용하다.
The cleaning liquid composition according to the present invention is a part of the photoresist composition to be dissolved (resist scum) or a rough part of the pattern (line width roughness) which is a problem when forming the photoresist pattern. : Part of which the numerical value of LWR) increased) can be removed by making it adsorb | suck to the said water-soluble polymer, and dissolving in solvents, such as water. In addition, it is possible to prevent the pattern collapse through the surfactant. Therefore, the cleaning liquid composition of the present invention is useful for forming fine patterns using extreme ultraviolet lithography (EUVL) technology.

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

본 발명에 따른 세정액 조성물은 하기 화학식 1로 표시되는 반복단위를 포함하는 수용성 고분자, 계면활성제, 및 용매를 포함한다.The cleaning liquid composition according to the present invention includes a water-soluble polymer, a surfactant, and a solvent including a repeating unit represented by the following Chemical Formula 1.

Figure pat00002
Figure pat00002

상기 화학식 1에서, R1은 수소 원자(H), 불소 원자(F), 메틸기(-CH3), 탄소수 1 내지 20, 바람직하게는 탄소수 1 내지 10의 불소화 알킬기 또는 탄소수 1 내지 5, 바람직하게는 탄소수 1 내지 4의 히드록시알킬기이고, R2는 존재하지 않거나, 탄소수 1 내지 20, 바람직하게는 탄소수 1 내지 10, 더욱 바람직하게는 1 내지 5의 알킬기이다.
In Chemical Formula 1, R 1 is a hydrogen atom (H), a fluorine atom (F), a methyl group (-CH 3 ), a C 1 to 20, preferably a C 1 to 10 fluorinated alkyl group or 1 to 5 carbon atoms, preferably Is a hydroxyalkyl group having 1 to 4 carbon atoms, R 2 is absent or an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

본 발명에 사용되는 수용성 고분자는 상기 화학식 1로 표시되는 반복단위를 상기 수용성 고분자를 구성하는 전체 반복단위에 대하여, 10 내지 100몰%, 바람직하게는 15 내지 80몰%, 더욱 바람직하게는 20 내지 50몰% 포함한다. 본 발명의 세정액 조성물은 1종 이상의 상기 수용성 고분자를 0.001 내지 5중량%, 바람직하게는 0.001 내지 1중량%, 더욱 바람직하게는 0.01 내지 0.5중량%, 가장 바람직하게는 0.05 내지 0.1중량% 포함함으로써, 상기 수용성 고분자가 포토레지스트 패턴 형성 시, 용해되어야 할 포토레지스트 조성물 중 부분적으로 용해되지 않은 부분(레지스트 스컴(scum))이나, 패턴의 거친 부분(선폭 거칠기(line width roughness: LWR)의 수치가 증대된 부분)에 흡착되어, 레지스트 스컴이나 패턴의 거친 부분이 용매에 용해될 수 있도록 한다. 상기 수용성 고분자는 상기 화학식 1로 표시되는 반복단위 단독으로 이루어진 호모폴리머(homopolymer)일 수 있으며, 상기 수용성 고분자를 구성하는 전체 반복단위에 대하여, 화학식 1로 표시되는 반복단위가 10몰% 미만이면, 수용성 고분자가 부분적으로 용해된 레지스트 부분, 즉, 레지스트 스컴이나 패턴의 거친 부분에 흡착이 안 될 우려가 있다. 또한, 전체 세정액 조성물에 대하여, 상기 수용성 고분자의 함량이 0.001중량% 미만이면, 수용성 고분자가 부분적으로 용해된 레지스트 부분, 즉, 레지스트 스컴이나 패턴의 거친 부분에 흡착이 안 될 우려가 있고, 5중량%를 초과하면, 세정 시, 레지스트 스컴이나 패턴의 거친 부분에 흡착된 고분자가 용매에 의해 용해되지 않아, 레지스트 스컴 등이 제거되지 않을 우려가 있다.
The water-soluble polymer used in the present invention is 10 to 100 mol%, preferably 15 to 80 mol%, more preferably 20 to 20 repeating units represented by the formula (1) to the total repeating units constituting the water-soluble polymer. Contains 50 mol%. The cleaning liquid composition of the present invention comprises 0.001 to 5% by weight, preferably 0.001 to 1% by weight, more preferably 0.01 to 0.5% by weight, most preferably 0.05 to 0.1% by weight of at least one water-soluble polymer, When the water-soluble polymer forms a photoresist pattern, a portion of the photoresist composition to be dissolved (resist scum) or a rough portion of the pattern (line width roughness (LWR)) increases. In this case, so that the resist scum or the rough portion of the pattern can be dissolved in the solvent. The water-soluble polymer may be a homopolymer consisting of a repeating unit represented by the formula (1) alone, with respect to all the repeating units constituting the water-soluble polymer, if the repeating unit represented by the formula (1) is less than 10 mol%, There is a possibility that the water-soluble polymer may not be adsorbed on the part of the resist partially dissolved, that is, the rough part of the resist scum or the pattern. If the content of the water-soluble polymer is less than 0.001% by weight with respect to the entire cleaning liquid composition, there is a fear that the water-soluble polymer may not be adsorbed to the part of the resist in which the water-soluble polymer is partially dissolved, that is, to the rough part of the resist scum or the pattern, and 5% by weight. When it exceeds%, the polymer adsorbed to the rough portion of the resist scum or pattern during the cleaning may not be dissolved by the solvent, and the resist scum or the like may not be removed.

상기 수용성 고분자의 구체적인 예로는, 하기 화학식 2로 표시되는 고분자를 예시할 수 있다.Specific examples of the water-soluble polymer may be a polymer represented by the following formula (2).

Figure pat00003
Figure pat00003

상기 화학식 2에서, R1은 각각 독립적으로, 수소 원자(H), 불소 원자(F), 메틸기(-CH3), 탄소수 1 내지 20, 바람직하게는 탄소수 1 내지 10의 불소화 알킬기 또는 탄소수 1 내지 5, 바람직하게는 탄소수 1 내지 4의 히드록시알킬기이고, R2는 각각 독립적으로, 존재하지 않거나, 탄소수 1 내지 20, 바람직하게는 탄소수 1 내지 10, 더욱 바람직하게는 1 내지 5의 알킬기이고, Z는 물에 대한 용해도를 증가시키기 위한 친수성 관능기로서, 수용성 고분자의 물에 대한 용해도를 증가시킬 수 있는 친수성 관능기를 특별한 제한 없이 사용할 수 있으며, 바람직하게는, 히드록시기(-OH), 카르복실기(-COOH), 아민기(-NH2) 등의 친수성 작용기이거나, 상기 친수성 작용기, 2차 및 3차 아민기(NH, N), 카보닐기(-CO-), 에스테르기(-COO-), 에테르기(-O-), 이들의 혼합물 등을 포함하는 탄소수 1 내지 10, 바람직하게는 탄소수 1 내지 6의 사슬형, 분지형 또는 고리형 탄화수소기이다. 상기 탄화수소기 Z는 알킬기 또는 아릴기일 수 있고, 상기 고리형 탄화수소기 Z의 구체적인 예로는, 피롤리디논, 이미다졸, 락탐 등을 예시할 수 있다. m 및 n은 상기 고분자를 구성하는 각 반복단위의 몰%로서, m은 10 내지 100몰%, 바람직하게는 15 내지 80몰%, 더욱 바람직하게는 20 내지 50몰%이고, n은 0 내지 90몰%, 바람직하게는 20 내지 85몰%, 더욱 바람직하게는 50 내지 80몰%이다. 상기 수용성 고분자는 m 반복단위(화학식 1로 표시되는 반복단위) 단독으로 이루어진 호모폴리머(homopolymer)일 수 있으며, m이 10몰% 미만이거나, n이 90몰%를 초과하면, 수용성 고분자가 부분적으로 용해된 레지스트 부분, 즉, 레지스트 스컴이나 패턴의 거친 부분에 흡착이 안 될 우려가 있다.
In Formula 2, R 1 is each independently a hydrogen atom (H), a fluorine atom (F), a methyl group (-CH 3 ), a C 1 to 20, preferably a C 1 to 10 fluorinated alkyl group or C 1 to 5, preferably a hydroxyalkyl group having 1 to 4 carbon atoms, R 2 are each independently, absent or an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, Z is a hydrophilic functional group for increasing the solubility in water, and can be used without particular limitation a hydrophilic functional group capable of increasing the solubility in water of the water-soluble polymer, preferably, a hydroxyl group (-OH), a carboxyl group (-COOH ), Or an hydrophilic functional group such as an amine group (-NH 2 ), or the hydrophilic functional group, secondary and tertiary amine groups (NH, N), carbonyl group (-CO-), ester group (-COO-), ether group Carbon number including (-O-), mixtures thereof and the like It is a 1-10, preferably C1-C6 linear, branched or cyclic hydrocarbon group. The hydrocarbon group Z may be an alkyl group or an aryl group, and specific examples of the cyclic hydrocarbon group Z may include pyrrolidinone, imidazole, lactam, and the like. m and n are mol% of each repeating unit constituting the polymer, m is 10 to 100 mol%, preferably 15 to 80 mol%, more preferably 20 to 50 mol%, n is 0 to 90 Mol%, preferably 20 to 85 mol%, more preferably 50 to 80 mol%. The water-soluble polymer may be a homopolymer consisting of m repeating units (repeating unit represented by Formula 1) alone, when m is less than 10 mol% or n is more than 90 mol%, the water-soluble polymer is partially There is a fear that adsorption may not occur on the dissolved resist portion, that is, the rough portion of the resist scum or pattern.

상기 화학식 2로 표시되는 고분자의 구체적인 예로는, 하기 화학식 2a 내지 2h로 표시되는 고분자를 예시할 수 있다.Specific examples of the polymer represented by Formula 2 may include a polymer represented by the following Formulas 2a to 2h.

[화학식 2a](2a)

Figure pat00004
Figure pat00004

[화학식 2b][Formula 2b]

Figure pat00005
Figure pat00005

[화학식 2c][Formula 2c]

Figure pat00006
Figure pat00006

[화학식 2d](2d)

Figure pat00007
Figure pat00007

[화학식 2e][Formula 2e]

Figure pat00008
Figure pat00008

[화학식 2f][Formula 2f]

Figure pat00009
Figure pat00009

[화학식 2g][Formula 2g]

Figure pat00010
Figure pat00010

[화학식 2h][Formula 2h]

Figure pat00011
Figure pat00011

상기 화학식 2a 내지 2h에서, m 및 n은 상기 화학식 2에서 정의한 바와 같다.
In Formulas 2a to 2h, m and n are as defined in Formula 2.

상기 수용성 고분자는, 공지의 유기 합성법에 의하여 제조될 수 있으며, 예를 들면, 하기 실시예에 나타낸 합성법을 응용하여 합성할 수 있다. 상기 수용성 고분자의 중량평균분자량(Mw)은 1,000 내지 100,000, 바람직하게는 1,500 내지 50,000, 더욱 바람직하게는 2,000 내지 10,000이다. 상기 수용성 고분자의 중량평균분자량이 1,000 미만이면, 수용성 고분자가 부분적으로 용해된 레지스트 부분, 즉, 레지스트 스컴이나 패턴의 거친 부분에 흡착이 안 될 우려가 있고, 중량평균분자량이 100,000 이상이면, 세정 시, 레지스트 스컴이나 패턴의 거친 부분에 흡착된 고분자가 용매에 의해 용해되지 않아, 레지스트 스컴 등이 제거되지 않을 우려가 있다.
The water-soluble polymer can be produced by a known organic synthesis method, for example, can be synthesized by applying the synthesis method shown in the following Examples. The weight average molecular weight (Mw) of the water-soluble polymer is 1,000 to 100,000, preferably 1,500 to 50,000, more preferably 2,000 to 10,000. When the weight average molecular weight of the water-soluble polymer is less than 1,000, there is a possibility that the water-soluble polymer may not be adsorbed to the part of the resist in which the water-soluble polymer is partially dissolved, that is, the rough portion of the resist scum or the pattern, and when the weight average molecular weight is 100,000 or more, There is a concern that the polymer adsorbed to the resist scum or the rough portion of the pattern will not be dissolved by the solvent and the resist scum or the like may not be removed.

본 발명에 사용되는 계면활성제는 세정액 조성물의 표면 장력을 낮추기 위한 것으로서, 예를 들면, 세정액 조성물을 스핀 드라이(spin-dry)시킬 때에 발생하는 패턴간의 응력을 낮춤으로써 패턴 쓰러짐(pattern collapse)을 억제한다. 상기 계면활성제로는 통상의 수용성 계면활성제를 사용할 수 있으며, 예를 들면, 수용성 음이온성 계면활성제, 수용성 비이온성 계면활성제, 수용성 양이온성 계면활성제, 수용성 양쪽성이온 계면활성제 등을 단독 또는 2종 이상 혼합하여 사용할 수 있다. 상기 수용성 음이온성 계면활성제의 구체적인 예로는, 라우릴황산트리에탄올아민, 라우릴황산암모늄, 트리에탄올아민폴리옥시에틸렌알킬에테르설페이트(triethanol amine polyoxyethylene alkyl ether sulfates) 등을 예시할 수 있고, 상기 수용성 비이온성 계면활성제로의 구체적인 예로는, 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌세틸에테르, 폴리옥시에틸렌스테아릴에테르, 폴리옥시에틸렌올레일에테르, 폴리옥시에틸렌고급알코올에테르, 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌노닐페닐에테르, 폴리옥시알킬렌알킬에테르, 폴리옥시에틸렌 유도체, 폴리옥시에틸렌소르비탄모노라울레이트, 폴리옥시에틸렌소르비탄모노팔미테이트, 폴리옥시에틸렌소르비탄모노스테아레이트, 폴리옥시에틸렌소르비탄트리스테아레이트, 폴리옥시에틸렌소르비탄모노올레에이트, 폴리옥시에틸렌소르비탄트리올레에이트, 테트라올레인산폴리옥시에틸렌소르비트, 폴리에틸렌글리콜모노라울레이트, 폴리에틸렌글리콜모노스테아레이트, 폴리에틸렌글리콜디스테아레이트, 폴리에틸렌글리콜모노올레에이트, 폴리옥시에틸렌알킬아민, 폴리옥시에틸렌 경화 피마자유, 알칸올아미드 등을 예시할 수 있고, 상기 수용성 양이온성 계면활성제로의 구체적인 예로는 코코낫아민아세테이트(coconutamine acetate), 스테아릴아민아세테이트(stearyl amine acetate) 등을 예시할 수 있으며, 상기 수용성 양쪽성 계면활성제의 구체적인 예로는, 라우릴베타인, 스테아릴베타인, 라우릴디메틸아민옥사이드(lauryl dimethyl amineoxide), 2-알킬-N-카르복시메틸-N-히드록시에틸이미다졸리늄베타인 등을 예시할 수 있다. 또한, 상용화된 계면활성제로서, 3M사의 NOVEC 4200, FC-4430 등, Dupont사의 FSN, FSO 등, Air-product사의 S-465, S-485W 등, Rhodia사의 25R2, L-62 등, NEOS사의 212M, 215M 등, DIC사의 F-410, F-477 등을 단독 또는 혼합하여 사용할 수 있다.The surfactant used in the present invention is to lower the surface tension of the cleaning liquid composition, and for example, suppresses pattern collapse by lowering stress between patterns generated when spin-drying the cleaning liquid composition. do. As the surfactant, a conventional water-soluble surfactant can be used. For example, a water-soluble anionic surfactant, a water-soluble nonionic surfactant, a water-soluble cationic surfactant, a water-soluble amphoteric surfactant or the like alone or in combination of two or more. It can be mixed and used. Specific examples of the water-soluble anionic surfactant include lauryl triethanolamine, ammonium lauryl sulfate, triethanol amine polyoxyethylene alkyl ether sulfates, and the like. Specific examples of the activator include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether, and polyoxy. Ethylene nonyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tree Stearate, polyoxyethylene sorbitan Monooleate, polyoxyethylene sorbitan trioleate, tetraoleic acid polyoxyethylene sorbitan, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamine , Polyoxyethylene cured castor oil, alkanolamide, and the like, and specific examples of the water-soluble cationic surfactant include coconut nut amine acetate, stearyl amine acetate, and the like. Specific examples of the water-soluble amphoteric surfactant may include laurylbetaine, stearylbetaine, lauryl dimethyl amineoxide, 2-alkyl-N-carboxymethyl-N-hydroxyethyl Imidazolinium betaine etc. can be illustrated. As commercially available surfactants, such as 3M's NOVEC 4200 and FC-4430, Dupont's FSN and FSO, Air-product's S-465 and S-485W, Rhodia's 25R2 and L-62, etc., NEOS's 212M , F-410, F-477, etc. of DIC Corporation, etc. can be used individually or in mixture.

전체 세정액 조성물에 대하여, 상기 계면활성제의 함량은 0.001 내지 5중량%, 바람직하게는 0.001 내지 1중량%, 더욱 바람직하게는 0.01 내지 0.5중량%, 가장 바람직하게는 0.05 내지 0.1중량%이다. 상기 수용성 고분자의 함량이 0.001중량% 미만이면, 패턴 쓰러짐이 발생할 우려가 있고, 5중량%를 초과하면, 특별한 장점은 없으며, 불순물로 작용할 우려가 있다.
With respect to the total cleaning liquid composition, the content of the surfactant is 0.001 to 5% by weight, preferably 0.001 to 1% by weight, more preferably 0.01 to 0.5% by weight, most preferably 0.05 to 0.1% by weight. If the content of the water-soluble polymer is less than 0.001% by weight, there is a fear that pattern collapse occurs, and when the content of the water-soluble polymer exceeds 5% by weight, there is no particular advantage, and there is a fear of acting as an impurity.

본 발명에 사용되는 용매는, 포토레지스트 패턴을 세정하기 위한 것으로서, 물(순수(pure water))을 사용할 수 있으며, 필요에 따라, 물과 수용성 유기 용매를 혼합한 혼합 용매를 사용할 수 있다. 상기 수용성 유기 용매로는, 1가(價) 또는 다가(多價) 알코올계 유기 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. 상기 용매는 본 발명에 따른 세정액 조성물의 상기 수용성 고분자 및 계면활성제를 제외한 나머지 성분이며, 상기 용매로서, 상기 혼합 용매를 사용 시, 상기 수용성 유기 용매의 함량은, 전체 용매에 대하여, 0.01 내지 50중량%, 바람직하게는 0.1 내지 20중량%이다. 상기 혼합 용매 사용 시, 상기 수용성 유기 용매의 함량이 전체 용매에 대하여 50중량%를 초과하면, 용매에 포토레지스트 패턴이 용해되어 패턴 왜곡 현상이 나타날 우려가 있다.
The solvent used in the present invention is for washing the photoresist pattern, and water (pure water) can be used, and a mixed solvent obtained by mixing water and a water-soluble organic solvent can be used, if necessary. As the water-soluble organic solvent, a monohydric or polyhydric alcohol-based organic solvent may be used, and the monohydric alcohol may be methanol, ethanol, propanol, isopropyl alcohol (IPA), or the like. The polyhydric alcohol may be exemplified by ethylene glycol, propylene glycol, diethylene glycol, glycerin, alkyl ether or esters thereof, and the like. The solvent is the remaining components except for the water-soluble polymer and the surfactant of the cleaning liquid composition according to the present invention, and when the mixed solvent is used as the solvent, the content of the water-soluble organic solvent is 0.01 to 50% by weight based on the total solvent. %, Preferably 0.1 to 20% by weight. When using the mixed solvent, if the content of the water-soluble organic solvent exceeds 50% by weight relative to the total solvent, the photoresist pattern is dissolved in the solvent may cause a pattern distortion phenomenon.

본 발명에 따른 세정액 조성물은, 통상적인 리소그래피 공정의 세정 공정에 사용될 수 있으며, 예를 들면, 하기 실시예에 나타낸 바와 같이, 포토레지스트 패턴을 현상한 후, 패턴을 세정할 때 사용할 수 있다. 본 발명의 세정액 조성물은 미세 패턴 형성 시 발생하는 레지스트 스컴(scum), 패턴 쓰러짐 등을 방지하고, 패턴 거칠기를 개선할 수 있으므로, 극자외선 리소그라피(extreme ultraviolet lithography: EUVL) 기술을 사용한 미세 패턴 형성에 유용하다.
The cleaning liquid composition according to the present invention can be used in the cleaning process of a conventional lithography process, and can be used for cleaning the pattern after developing the photoresist pattern, for example, as shown in the following examples. Since the cleaning liquid composition of the present invention can prevent resist scum, pattern collapse, and the like, and improve pattern roughness, which is generated when forming a fine pattern, the cleaning liquid composition may be used for forming a fine pattern using extreme ultraviolet lithography (EUVL) technology. useful.

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.

[실시예 1] 화학식 1a로 표시되는 모노머 합성 Example 1 Synthesis of Monomer Represented by Chemical Formula 1a

500ml 2구(neck) 플라스크에 자석 교반 막대를 넣은 후, 아미노메탄술포닉산(amino methanesulfonic acid,

Figure pat00012
) 30g(0.27mol)을 넣고, 아세토니트릴(acetonitrile(ACN), CH3CN) 100g을 넣은 다음 0℃에서 교반하였다. 아크로일클로라이드(acroylchloride,
Figure pat00013
) 20g(0.22mol) 및 트리에틸아민 (triethylamine) 27g(0.27mol)을 아세토니트릴 100g에 녹여 적하 깔때기에 넣고, 상기 아미노메탄술포닉산 용액에 서서히 적하하였다. 적하 후, 상온에서 8시간 동안 반응시켰다. 반응 종료 후, 에틸아세테이트(ethylacetate) 50g을 넣고, 50g의 물을 이용하여 3회 반복 추출하고, 감압 하에서 용매를 제거하여, 하기 화학식 1a로 표시되는 모노머(화학식 1로 표시되는 반복 단위의 R1이 수소 원자(H)이고, R2가 메틸렌기(-CH2-)인 경우의 모노머) 26.2g을 얻었다{수율 72%, NMR: NH(8.23, s), CH2(5.42, s), acryl-CH2(5.6, 6.1, d), acryl-CH(6.52, dd)}.After putting a magnetic stir bar into a 500 ml two-neck flask, amino methanesulfonic acid,
Figure pat00012
) 30 g (0.27 mol) was added thereto, 100 g of acetonitrile (ACN, CH 3 CN) was added thereto, followed by stirring at 0 ° C. Acroylchloride (acroylchloride,
Figure pat00013
20 g (0.22 mol) and 27 g (0.27 mol) of triethylamine were dissolved in 100 g of acetonitrile and placed in a dropping funnel, and slowly added dropwise to the aminomethanesulphonic acid solution. After dropping, the mixture was reacted at room temperature for 8 hours. After the reaction was completed, 50 g of ethylacetate was added, the extract was repeatedly extracted three times with 50 g of water, and the solvent was removed under reduced pressure, and the monomer represented by the following Chemical Formula 1a (R 1 of the repeating unit represented by Chemical Formula 1) was used. This hydrogen atom (H), and 26.2 g of monomers when R 2 is a methylene group (-CH 2- ) were obtained (yield 72%, NMR: NH (8.23, s), CH 2 (5.42, s), acryl-CH 2 (5.6, 6.1, d), acryl-CH (6.52, dd)}.

[화학식 1a][Formula 1a]

Figure pat00014

Figure pat00014

[실시예 2 내지 11] 화학식 2a 내지 2h로 표시되는 고분자 합성 Examples 2 to 11 Polymer synthesis represented by Chemical Formulas 2a to 2h

하기 표 1의 조성에 따라, 상기 실시예 1에서 제조한 화학식 1a로 표시되는 모노머(m 모노머)와 각각의 상기 화학식 2a 내지 2h로 표시되는 고분자의 n 반복단위의 모노머(n 모노머:

Figure pat00015
,
Figure pat00016
,
Figure pat00017
,
Figure pat00018
,
Figure pat00019
,
Figure pat00020
,
Figure pat00021
및
Figure pat00022
)를 하기 표 1의 몰비율(m:n = 50몰%:50몰%, 20몰%:80몰% 또는 80몰%:20몰%)로 반응용매인 아세토니트릴(ACN)에 녹인 후, 질소 가스 분위기 하에서, 전체 모노머 100중량부에 대하여, 20중량부의 개시제 아조비스 (이소부티로니트릴)(AIBN)을 추가하고 혼합한 후, 반응물을 70℃에서 4시간 동안 중합시켰다. 중합 완료 후, 과량의 디에틸에테르(diethyl ether)에 반응 용액을 천천히 떨어뜨려 침전시키고, 침전물을 다시 아세토니트릴에 용해시킨 후, 디에틸에테르에 재침전시켜 화학식 2a 내지 2h로 표시되는 고분자를 얻었다. 얻어진 고분자의 중량평균분자량(Mw), 다분산지수(polydispersity index: PDI) 및 수율을 하기 표 1에 나타내었다.According to the composition of Table 1, the monomer (m monomer) represented by Formula 1a prepared in Example 1 and the monomer of n repeat units of the polymer represented by each of the formulas 2a to 2h (n monomer:
Figure pat00015
,
Figure pat00016
,
Figure pat00017
,
Figure pat00018
,
Figure pat00019
,
Figure pat00020
,
Figure pat00021
And
Figure pat00022
) Was dissolved in acetonitrile (ACN) as a reaction solvent in the molar ratio (m: n = 50 mol%: 50 mol%, 20 mol%: 80 mol% or 80 mol%: 20 mol%) of Table 1 below. Under a nitrogen gas atmosphere, 20 parts by weight of initiator azobis (isobutyronitrile) (AIBN) was added and mixed with respect to 100 parts by weight of the total monomer, and the reaction was then polymerized at 70 ° C. for 4 hours. After the completion of the polymerization, the reaction solution was slowly dropped into an excess of diethyl ether to precipitate the precipitate, and the precipitate was dissolved in acetonitrile again and then precipitated again in diethyl ether to obtain a polymer represented by Chemical Formulas 2a to 2h. . The weight average molecular weight (Mw), polydispersity index (PDI) and yield of the obtained polymer are shown in Table 1 below.

화학식Chemical formula m
모노머m
Monomer n
모노머n
Monomer m:n 몰비율m: n molar ratio 개시제 (AIBN)Initiator (AIBN) 반응용매(ACN)Reaction Solvent (ACN) MwMw PDIPDI 수율yield 실시예 2Example 2 2a2a 40g40g 10.7g10.7 g 50:5050:50 10.1g10.1 g 300g300 g 84008400 1.521.52 60%60% 실시예 3Example 3 2b2b 40g40g 17.5g17.5 g 50:5050:50 11.5g11.5 g 300g300 g 88008800 1.481.48 52%52% 실시예 4Example 4 2c2c 40g40g 28.1g28.1 g 50:5050:50 13.6g13.6 g 300g300 g 92009200 1.541.54 50%50% 실시예 5Example 5 2d2d 40g40g 13.8g13.8 g 50:5050:50 10.8g10.8 g 300g300 g 54005400 1.51.5 43%43% 실시예 6Example 6 2e2e 40g40g 20.6g20.6 g 50:5050:50 12.1g12.1 g 300g300 g 74007400 1.511.51 52%52% 실시예 7Example 7 2f2f 40g40g 26.9g26.9 g 50:5050:50 13.4g13.4g 300g300 g 1050010500 1.621.62 77%77% 실시예 8Example 8 2g2 g 40g40g 33.7g33.7 g 50:5050:50 14.7g14.7g 300g300 g 1120011200 1.641.64 75%75% 실시예 9Example 9 2h2h 40g40g 22.8g22.8 g 50:5050:50 12.6g12.6 g 300g300 g 1254012540 1.651.65 80%80% 실시예 10Example 10 2h2h 20g20g 45.6g45.6 g 20:8020:80 13.1g13.1 g 300g300 g 1002010020 1.621.62 64%64% 실시예 11Example 11 2h2h 60g60 g 8.5g8.5 g 80:2080:20 13.7g13.7 g 300g300 g 98509850 1.521.52 45%45%

[실시예 12] 포토레지스트용 감광성 고분자 합성 Example 12 Photosensitive Polymer Synthesis for Photoresist

2-메틸-2-아다만틸 메타크릴레이트 117.2g(0.5mol), 3-히드록시-1-아다만틸 메타크릴레이트 23.6g(0.1mol), 노보닐락톤 메타크릴레이트(제조사: 오사카 유키, 일본, 제품명: MNBL, 5-oxo-4-oxatricyclo[4,2,1,0] nonan-2-yl methacrylate) 88.9g(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).
2-methyl-2-adamantyl methacrylate 117.2g (0.5mol), 3-hydroxy-1-adamantyl methacrylate 23.6g (0.1mol), norbornyllactone methacrylate (manufacturer: Yuki Osaka , Japan, Product name: MNBL, 88.9 g (0.4 mol) of 5-oxo-4-oxatricyclo [4,2,1,0] nonan-2-yl methacrylate) and 6.6 g of azobis (isobutyronitrile) (AIBN) Was dissolved in 125 g of anhydrous tetrahydrofuran (THF), the gas was removed 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).

[실시예 13 내지 78 및 비교예 1 내지 2] 세정액 조성물 제조 및 평가 [Examples 13 to 78 and Comparative Examples 1 and 2] Preparation and Evaluation of Cleaning Liquid Composition

A. 세정액 조성물의 제조A. Preparation of Cleaning Liquid Composition

하기 표 2 내지 7의 조성에 따라, 수용성 고분자로서, 상기 실시예 2 내지 11에서 제조한 화학식 2a 내지 2h로 표시되는 고분자를 사용하고, 계면활성제로서, 라우릴디메틸아민옥사이드(lauryldimethylamine oxide: RDMAO), 3M사의 NOVEC 4200 및 FC-4430, Dupont사의 FSN 및 FSO, Air-product사의 S-465 및 S-485W, Rhodia사의 25R2 및 L-62, NEOS사의 212M 및 215M, 또는 DIC사의 F-410 및 F-477을 사용하고, 용매로서 순수 또는 순수 및 알코올류 용매(이소프로필 알코올(isopropyl alcohol: IPA), 메탄올 또는 에탄올)의 혼합 용매를 사용하였으며, 상기 수용성 고분자 및 계면활성제를 상기 혼합 용매에 4시간 동안 녹인 후, 0.1㎛ 크기의 기공을 갖는 수용성 필터로 여과하여 세정액 조성물(실시예 11 내지 66)을 제조하였다.
According to the composition of Tables 2 to 7, as the water-soluble polymer, using the polymer represented by the formula 2a to 2h prepared in Examples 2 to 11, as a surfactant, lauryldimethylamine oxide (lauryldimethylamine oxide: RDMAO) 3M's NOVEC 4200 and FC-4430, Dupont's FSN and FSO, Air-product's S-465 and S-485W, Rhodia's 25R2 and L-62, NEOS's 212M and 215M, or DIC's F-410 and F -477 was used, and a mixed solvent of pure or pure water and an alcohol solvent (isopropyl alcohol (IPA), methanol or ethanol) was used as the solvent, and the water-soluble polymer and the surfactant were added to the mixed solvent for 4 hours. After dissolving for a while, the cleaning solution composition (Examples 11 to 66) was prepared by filtration with a water-soluble filter having pores of 0.1 μm in size.

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

(a) 상기 실시예 12에서 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.
(a) As the photosensitive polymer synthesized in Example 12, a photoacid generator, 10 parts by weight of diphenyl paratoluenylsulfonium nona plate (TPS-NF), base stabilizer (quencher) to 100 parts by weight of the photosensitive polymer 20 parts by weight of triethanolamine based on 100 parts by weight of the photoacid generator was added to propylene glycol monomethyl ether acetate (PGMEA) and stirred for at least 12 hours to completely dissolve, and then a nylon filter having a pore size of 0.01 μm and polytetrafluoro A photoresist composition was prepared by sequentially filtering a filter made of a polytetrafluoroethylene (PTFE) material.

(b) 제조된 포토레지스트 조성물을, 실리콘 웨이퍼의 피식각층 상부에 스핀 코팅하여, 포토레지스트 박막(필름)을 형성한 다음, 100℃에서 60초 동안 가열(프리베이킹 (prebaking))하고, (i) 개구수(Numerical Aperture: N.A.) 0.85인 ArF ASML 1200B 장비로 노광하거나, (ii) 극자외선 리소그라피(extreme ultraviolet lithography: EUVL) 노광기로 노광한 다음, 125℃에서 60초 동안 가열(post exposure bake: PEB)하였다. 이렇게 베이크(가열)한 웨이퍼를 2.38중량%의 테트라메틸암모늄 히드록사이드(TMAH) 수용액으로 30초간 현상함으로써, (i) 필름 두께 140nm, 선폭 70nm 의 1 : 1 라인 및 스페이스(L/S: line/space) 패턴(비교예 1) 또는 (ii) 필름 두께 60nm, 선폭 30nm 의 1 : 1 라인 및 스페이스(L/S: line/space) 패턴(비교예 2)을 형성하였다. 형성된 포토레지스트 패턴의 패턴 쓰러짐 및 선폭 거칠기(line width roughness: LWR)를 평가하여, 하기 표 2 및 7에 나타내었다. 상기 포토레지스트 필름 두께는 KLA사의 계측장비인 Opti-2600을 사용하여 측정하였고, 전자현미경(Critical Dimension Scanning Electron Microscope: CD-SEM)으로는 Hitachi사의 S9220 장비를 사용하여, 패턴의 패턴 쓰러짐 선폭(단위: nm) 및 선폭 거칠기(LWR, 단위: nm)를 측정하였다. 여기서, 패턴 쓰러짐의 판단기준은 L/S 패턴의 맨 끝 가장 자리 패턴이 쓰러지는 포인트(point)를 측정하여 산출하였다. 또한, 선폭이 아닌 바닥(bottom)에 존재하는 레지스트 스컴(scum)도 선폭 거칠기(LWR) 수치에 영향을 주므로, 선폭 거칠기(LWR)가 개선(감소)된다는 것은 레지스트 스컴(scum)도 개선됨을 의미한다.
(b) spin-coating the prepared photoresist composition on the etching target layer of the silicon wafer to form a photoresist thin film (film), and then heating (prebaking) at 100 ° C. for 60 seconds, and (i Exposure to an ArF ASML 1200B instrument with a Numerical Aperture (NA) of 0.85, or (ii) exposure to an extreme ultraviolet lithography (EUVL) exposure, followed by a post exposure bake of 60 seconds at 125 ° C. PEB). This baked (heated) wafer was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, thereby (i) 1: 1 line and space (L / S: line) having a film thickness of 140 nm and a line width of 70 nm. / space) pattern (Comparative Example 1) or (ii) 1: 1 line and space (L / S: line / space) pattern (Comparative Example 2) having a film thickness of 60 nm and a line width of 30 nm. The pattern collapse and line width roughness (LWR) of the formed photoresist pattern were evaluated, and are shown in Tables 2 and 7 below. The photoresist film thickness was measured using a KLA company's measurement equipment, Opti-2600, and using a Hitachi S9220 device as a critical dimension scanning electron microscope (CD-SEM), pattern collapse line width (unit) : nm) and line width roughness (LWR, unit: nm) were measured. Here, the criterion of the pattern collapse was calculated by measuring the point at which the end edge pattern of the L / S pattern falls. In addition, since the resist scum present at the bottom of the line width also affects the numerical value of the line width roughness (LWR), the improvement (decrease) of the line width roughness (LWR) also means that the resist scum is also improved. do.

(C) 또한, 상기 (b) 단계와 동일하게 포토레지스트 패턴을 현상한 다음, 순수로 30초 동안 세정하고, 상기 A 단계에서 제조한 세정액 조성물을 현상된 포토레지스트 패턴 표면에 뿌리고 15초 동안 접촉시킨 다음, 스핀 드라이를 통해서 웨이퍼를 건조하여 (i) 필름 두께 140nm, 선폭 70nm 의 1 : 1 라인 및 스페이스(L/S: line/space) 패턴(실시예 13 내지 70의 세정액 조성물 사용) 또는 (ii) 필름 두께 60nm, 선폭 30nm 의 1 : 1 라인 및 스페이스(L/S: line/space) 패턴(실시예 70 내지 78의 세정액 조성물 사용)을 형성하였다. 상기 (b) 단계와 동일한 방법으로 형성된 포토레지스트 패턴의 패턴 쓰러짐 선폭(단위: nm) 및 선폭 거칠기(LWR, 단위: nm)를 평가하여, 하기 표 2 내지 7에 나타내었다. 표 2 내지 6는 (i) ArF 노광기를 사용한 실험 결과이며, 표 7은 (ii) 극자외선 리소그라피(EUVL) 노광기를 사용하여 얻은 실험 결과이다. 비교예 1 내지 2는 본 발명에 따른 세정액을 사용하지 않는 공정, 즉, 순수로만 패턴을 세정한 실험의 측정 결과이다.(C) In addition, after developing the photoresist pattern in the same manner as in the step (b), and then washed with pure water for 30 seconds, spraying the cleaning liquid composition prepared in step A on the surface of the developed photoresist pattern and contacted for 15 seconds The wafer was then dried by spin drying to (i) 1: 1 line and space (L / S: line / space) pattern (using the cleaning liquid composition of Examples 13 to 70) having a film thickness of 140 nm and a line width of 70 nm, or ( ii) A 1: 1 line and a space (L / S: line / space) pattern (using the cleaning liquid compositions of Examples 70 to 78) having a film thickness of 60 nm and a line width of 30 nm were formed. The pattern collapse line width (unit: nm) and line width roughness (LWR, unit: nm) of the photoresist pattern formed in the same manner as in the step (b) were evaluated, and are shown in Tables 2 to 7 below. Tables 2 to 6 show experimental results using the (i) ArF exposure machine, and Table 7 shows the experimental results obtained using the (ii) extreme ultraviolet lithography (EUVL) exposure machine. Comparative Examples 1 and 2 are measurement results of a step of not using the cleaning liquid according to the present invention, that is, an experiment in which the pattern was washed only with pure water.

수용성 고분자Water soluble polymer 계면활성제Surfactants 용매비율
(순수: 알코올)Solvent Ratio
(Pure: alcohol) 패턴 쓰러짐 선폭Pattern collapse line width 선폭 거칠기Line width roughness 실시예Example 함량(ppm)Content (ppm) 명칭designation 함량(ppm)Content (ppm) 알코올Alcohol 비율ratio 비교예 1Comparative Example 1 -- -- -- -- -- 100:0100: 0 74 nm74 nm 5.4 nm5.4 nm 실시예 13Example 13 22 10001000 RDMAORDMAO 10001000 -- 100:0100: 0 60 nm60 nm 3.8 nm3.8 nm 실시예 14Example 14 33 10001000 RDMAORDMAO 10001000 -- 100:0100: 0 61 nm61 nm 4.2 nm4.2 nm 실시예 15Example 15 44 10001000 RDMAORDMAO 10001000 -- 100:0100: 0 62 nm62 nm 4.3 nm4.3 nm 실시예 16Example 16 55 10001000 RDMAORDMAO 10001000 -- 100:0100: 0 65 nm65 nm 4.0 nm4.0 nm 실시예 17Example 17 66 10001000 RDMAORDMAO 10001000 -- 100:0100: 0 62 nm62 nm 4.1 nm4.1 nm 실시예 18Example 18 77 10001000 RDMAORDMAO 10001000 -- 100:0100: 0 59 nm59 nm 4.1 nm4.1 nm 실시예 19Example 19 88 10001000 RDMAORDMAO 10001000 -- 100:0100: 0 63 nm63 nm 3.8 nm3.8 nm 실시예 20Example 20 99 10001000 RDMAORDMAO 10001000 -- 100:0100: 0 62 nm62 nm 3.6 nm3.6 nm 실시예 21Example 21 33 100 100 RDMAORDMAO 1000 1000 -- 100:0100: 0 68 nm68 nm 4.8 nm4.8 nm 실시예 22Example 22 33 500 500 RDMAORDMAO 1000 1000 -- 100:0100: 0 65 nm65 nm 4.5 nm4.5 nm 실시예 23Example 23 33 2000 2000 RDMAORDMAO 1000 1000 -- 100:0100: 0 60 nm60 nm 4.0 nm4.0 nm 실시예 24Example 24 33 5000 5000 RDMAORDMAO 1000 1000 -- 100:0100: 0 59 nm59 nm 3.9 nm3.9 nm

수용성 고분자Water soluble polymer 계면활성제Surfactants 용매비율
(순수: 알코올)Solvent Ratio
(Pure: alcohol) 패턴 쓰러짐 선폭Pattern collapse line width 선폭 거칠기Line width roughness 실시예Example 함량(ppm)Content (ppm) 명칭designation 함량(ppm)Content (ppm) 알코올Alcohol 비율ratio 실시예 25Example 25 33 1000 1000 Novec 4200Novec 4200 1000 1000 -- 100:0100: 0 63 nm63 nm 4.3 nm4.3 nm 실시예 26Example 26 33 1000 1000 FC-4430FC-4430 1000 1000 -- 100:0100: 0 62 nm62 nm 4.3 nm4.3 nm 실시예 27Example 27 33 1000 1000 FSNFSN 1000 1000 -- 100:0100: 0 63 nm63 nm 4.2 nm4.2 nm 실시예 28Example 28 33 1000 1000 FSOFSO 1000 1000 -- 100:0100: 0 64 nm64 nm 4.2 nm4.2 nm 실시예 29Example 29 33 1000 1000 S-465S-465 1000 1000 -- 100:0100: 0 64 nm64 nm 4.1 nm4.1 nm 실시예 30Example 30 33 1000 1000 S-485WS-485W 1000 1000 -- 100:0100: 0 63 nm63 nm 4.2 nm4.2 nm 실시예 31Example 31 33 1000 1000 25R225R2 1000 1000 -- 100:0100: 0 63 nm63 nm 4.5 nm4.5 nm 실시예 32Example 32 33 1000 1000 L-62L-62 1000 1000 -- 100:0100: 0 62 nm62 nm 4.2 nm4.2 nm 실시예 33Example 33 33 1000 1000 212M212M 1000 1000 -- 100:0100: 0 63 nm63 nm 4.2 nm4.2 nm 실시예 34Example 34 33 1000 1000 215M215M 1000 1000 -- 100:0100: 0 63 nm63 nm 4.3 nm4.3 nm 실시예 35Example 35 33 1000 1000 F-410F-410 1000 1000 -- 100:0100: 0 62 nm62 nm 4.3 nm4.3 nm 실시예 36Example 36 33 1000 1000 F-477F-477 1000 1000 -- 100:0100: 0 63 nm63 nm 4.2 nm4.2 nm

수용성 고분자Water soluble polymer 계면활성제Surfactants 용매비율
(순수: 알코올)Solvent Ratio
(Pure: alcohol) 패턴 쓰러짐 선폭Pattern collapse line width 선폭 거칠기Line width roughness 실시예Example 함량(ppm)Content (ppm) 명칭designation 함량(ppm)Content (ppm) 알코올Alcohol 비율ratio 실시예 37Example 37 88 1000 1000 Novec 4200Novec 4200 1000 1000 -- 100:0100: 0 58 nm58 nm 4.0 nm4.0 nm 실시예 38Example 38 88 1000 1000 FC-4430FC-4430 1000 1000 -- 100:0100: 0 58 nm58 nm 3.9 nm3.9 nm 실시예 39Example 39 88 1000 1000 FSNFSN 1000 1000 -- 100:0100: 0 58 nm58 nm 3.9 nm3.9 nm 실시예 40Example 40 88 1000 1000 FSOFSO 1000 1000 -- 100:0100: 0 59 nm59 nm 3.9 nm3.9 nm 실시예 41Example 41 88 1000 1000 S-465S-465 1000 1000 -- 100:0100: 0 59 nm59 nm 4.0 nm4.0 nm 실시예 42Example 42 88 1000 1000 S-485WS-485W 1000 1000 -- 100:0100: 0 60 nm60 nm 4.0 nm4.0 nm 실시예 43Example 43 88 1000 1000 25R225R2 1000 1000 -- 100:0100: 0 61 nm61 nm 4.0 nm4.0 nm 실시예 44Example 44 88 1000 1000 L-62L-62 1000 1000 -- 100:0100: 0 59 nm59 nm 4.0 nm4.0 nm 실시예 45Example 45 88 1000 1000 212M212M 1000 1000 -- 100:0100: 0 58 nm58 nm 3.9 nm3.9 nm 실시예 46Example 46 88 1000 1000 215M215M 1000 1000 -- 100:0100: 0 60 nm60 nm 3.8 nm3.8 nm 실시예 47Example 47 88 1000 1000 F-410F-410 1000 1000 -- 100:0100: 0 60 nm60 nm 3.9 nm3.9 nm 실시예 48Example 48 88 1000 1000 F-477F-477 1000 1000 -- 100:0100: 0 60 nm60 nm 3.8 nm3.8 nm

수용성 고분자Water soluble polymer 계면활성제Surfactants 용매비율
(순수: 알코올)Solvent Ratio
(Pure: alcohol) 패턴 쓰러짐 선폭Pattern collapse line width 선폭 거칠기Line width roughness 실시예Example 함량(ppm)Content (ppm) 명칭designation 함량(ppm)Content (ppm) 알코올Alcohol 비율ratio 실시예 49Example 49 99 1000 1000 Novec 4200Novec 4200 1000 1000 -- 100:0100: 0 58 nm58 nm 3.7 nm3.7 nm 실시예 50Example 50 99 1000 1000 FC-4430FC-4430 1000 1000 -- 100:0100: 0 58 nm58 nm 3.7 nm3.7 nm 실시예 51Example 51 99 1000 1000 FSNFSN 1000 1000 -- 100:0100: 0 57 nm57 nm 3.8 nm3.8 nm 실시예 52Example 52 99 1000 1000 FSOFSO 1000 1000 -- 100:0100: 0 57 nm57 nm 3.8 nm3.8 nm 실시예 53Example 53 99 1000 1000 S-465S-465 1000 1000 -- 100:0100: 0 58 nm58 nm 3.8 nm3.8 nm 실시예 54Example 54 99 1000 1000 S-485WS-485W 1000 1000 -- 100:0100: 0 59 nm59 nm 3.7 nm3.7 nm 실시예 55Example 55 99 1000 1000 25R225R2 1000 1000 -- 100:0100: 0 59 nm59 nm 3.7 nm3.7 nm 실시예 56Example 56 99 1000 1000 L-62L-62 1000 1000 -- 100:0100: 0 59 nm59 nm 3.8 nm3.8 nm 실시예 57Example 57 99 1000 1000 212M212M 1000 1000 -- 100:0100: 0 58 nm58 nm 4.0 nm4.0 nm 실시예 58Example 58 99 1000 1000 215M215M 1000 1000 -- 100:0100: 0 57 nm57 nm 4.0 nm4.0 nm 실시예 59Example 59 99 1000 1000 F-410F-410 1000 1000 -- 100:0100: 0 57 nm57 nm 3.9 nm3.9 nm 실시예 60Example 60 99 1000 1000 F-477F-477 1000 1000 -- 100:0100: 0 58 nm58 nm 3.8 nm3.8 nm

수용성 고분자Water soluble polymer 계면활성제Surfactants 용매비율
(순수: 알코올)Solvent Ratio
(Pure: alcohol) 패턴 쓰러짐 선폭Pattern collapse line width 선폭 거칠기Line width roughness 실시예Example 함량(ppm)Content (ppm) 명칭designation 함량(ppm)Content (ppm) 알코올Alcohol 비율ratio 실시예 61Example 61 99 1000 1000 RDMAORDMAO 1000 1000 메탄올Methanol 90:1090:10 62 nm62 nm 3.9 nm3.9 nm 실시예 62Example 62 99 1000 1000 RDMAORDMAO 1000 1000 메탄올Methanol 70:3070:30 63 nm63 nm 3.9 nm3.9 nm 실시예 63Example 63 99 1000 1000 RDMAORDMAO 1000 1000 에탄올ethanol 90:1090:10 63 nm63 nm 4.0 nm4.0 nm 실시예 64Example 64 99 1000 1000 RDMAORDMAO 1000 1000 에탄올ethanol 70:3070:30 62 nm62 nm 4.0 nm4.0 nm 실시예 65Example 65 99 1000 1000 RDMAORDMAO 1000 1000 IPAIPA 90:1090:10 63 nm63 nm 4.0 nm4.0 nm 실시예 66Example 66 99 1000 1000 RDMAORDMAO 1000 1000 IPAIPA 70:3070:30 58 nm58 nm 4.0 nm4.0 nm 실시예 67Example 67 1010 1000 1000 RDMAORDMAO 1000 1000 -- 100:0100: 0 62 nm62 nm 3.8 nm3.8 nm 실시예 68Example 68 1111 1000 1000 RDMAORDMAO 1000 1000 -- 100:0100: 0 62 nm62 nm 3.9 nm3.9 nm 실시예 69Example 69 1010 1000 1000 RDMAORDMAO 1000 1000 IPAIPA 90:1090:10 61 nm61 nm 3.8 nm3.8 nm 실시예 70Example 70 1111 10001000 RDMAORDMAO 10001000 IPAIPA 90:1090:10 60 nm60 nm 3.8 nm3.8 nm

수용성 고분자Water soluble polymer 계면활성제Surfactants 용매비율
(순수: 알코올)Solvent Ratio
(Pure: alcohol) 패턴 쓰러짐 선폭Pattern collapse line width 선폭 거칠기Line width roughness 실시예Example 함량(ppm)Content (ppm) 명칭designation 함량(ppm)Content (ppm) 알코올Alcohol 비율ratio 비교예 2Comparative Example 2 -- - - RDMAORDMAO 1000 1000 -- 100:0100: 0 24 nm24 nm 5.5 nm5.5 nm 실시예 71Example 71 22 1000 1000 RDMAORDMAO 1000 1000 -- 100:0100: 0 20 nm20 nm 4.3 nm4.3 nm 실시예 72Example 72 33 1000 1000 RDMAORDMAO 1000 1000 -- 100:0100: 0 20 nm20 nm 4.8 nm4.8 nm 실시예 73Example 73 44 1000 1000 RDMAORDMAO 1000 1000 -- 100:0100: 0 21 nm21 nm 4.7 nm4.7 nm 실시예 74Example 74 55 1000 1000 RDMAORDMAO 1000 1000 -- 100:0100: 0 20 nm20 nm 4.3 nm4.3 nm 실시예 75Example 75 66 1000 1000 RDMAORDMAO 1000 1000 -- 100:0100: 0 21 nm21 nm 4.3 nm4.3 nm 실시예 76Example 76 77 1000 1000 RDMAORDMAO 1000 1000 -- 100:0100: 0 20 nm20 nm 4.3 nm4.3 nm 실시예 77Example 77 88 1000 1000 RDMAORDMAO 1000 1000 -- 100:0100: 0 20 nm20 nm 4.8 nm4.8 nm 실시예 78Example 78 99 1000 1000 RDMAORDMAO 1000 1000 -- 100:0100: 0 20 nm20 nm 5.0 nm5.0 nm

상기 표 2 내지 7으로부터, 본 발명에 따른 세정액 조성물은 수용성 고분자의 함량이 증가할수록 패턴 쓰러짐 선폭 및 선폭 거칠기(LWR)가 감소하여, 패턴 쓰러짐 및 레지스트 스컴이 방지되고, 선폭 거칠기의 수치 증대가 억제됨을 알 수 있고(실시예 14 및 실시예 21 내지 24), 상용화된 계면활성제들과의 조합에서도 좋은 결과를 보이고 있음을 알 수 있다. 또한, (i) ArF 노광기를 이용하거나 (ii) EUVL 노광기를 이용한 경우 모두에서, 세정액 조성물을 사용하지 않은 경우(비교예 1 및 2)에 비하여, 패턴 쓰러짐 선폭 및 선폭 거칠기가 감소하여, 패턴 쓰러짐 및 레지스트 스컴이 방지되고, 선폭 거칠기의 수치 증대가 억제됨을 알 수 있다.From Tables 2 to 7, the cleaning liquid composition according to the present invention, the pattern collapse line width and line width roughness (LWR) decreases as the content of the water-soluble polymer increases, thereby preventing pattern collapse and resist scum, and increasing the numerical value of the line width roughness. (Examples 14 and 21 to 24), and in combination with commercially available surfactants can be seen that good results. In addition, in both the case of (i) using the ArF exposure machine or (ii) the EUVL exposure machine, the pattern collapse line width and the line width roughness were reduced and the pattern collapsed, as compared with the case where no cleaning liquid composition was used (Comparative Examples 1 and 2). And resist scum is prevented, and it turns out that the numerical increase of line | wire width roughness is suppressed.

Claims (6)

하기 화학식 1로 표시되는 반복단위를 포함하는 수용성 고분자;
계면활성제; 및
용매를 포함하는 세정액 조성물.
[화학식 1]
Figure pat00023

상기 화학식 1에서, R1은 수소 원자(H), 불소 원자(F), 메틸기(-CH3), 탄소수 1 내지 20의 불소화 알킬기 또는 탄소수 1 내지 5의 히드록시알킬기이고, R2는 존재하지 않거나, 탄소수 1 내지 20의 알킬기이다.A water-soluble polymer comprising a repeating unit represented by the formula (1);
Surfactants; And
Cleaning liquid composition comprising a solvent.
[Formula 1]
Figure pat00023

In Formula 1, R 1 is a hydrogen atom (H), a fluorine atom (F), a methyl group (-CH 3 ), a fluorinated alkyl group of 1 to 20 carbon atoms or a hydroxyalkyl group of 1 to 5 carbon atoms, R 2 is not present Or an alkyl group having 1 to 20 carbon atoms. 제1항에 있어서, 상기 수용성 고분자의 함량은 전체 세정액 조성물에 대하여 0.001 내지 5중량%이고, 상기 계면활성제의 함량은 전체 세정액 조성물에 대하여 0.001 내지 5중량%이며, 나머지 성분은 용매인 것인 세정액 조성물.According to claim 1, wherein the content of the water-soluble polymer is 0.001 to 5% by weight based on the total cleaning solution composition, the content of the surfactant is 0.001 to 5% by weight based on the total cleaning solution composition, the remaining components are the solvent Composition. 제1항에 있어서, 상기 수용성 고분자의 중량평균분자량은 1,000 내지 100,000이고, 상기 수용성 고분자를 구성하는 전체 반복단위에 대하여, 상기 화학식 1로 표시되는 반복단위의 몰%는 10 내지 100몰%인 것인 세정액 조성물.The method of claim 1, wherein the weight average molecular weight of the water-soluble polymer is 1,000 to 100,000, the mole% of the repeating unit represented by the formula (1) is 10 to 100 mol% with respect to all the repeating units constituting the water-soluble polymer. Phosphorus cleaning liquid composition. 제1항에 있어서, 상기 수용성 고분자는 하기 화학식 2로 표시되는 고분자인 것인 세정액 조성물.
[화학식 2]
Figure pat00024

상기 화학식 2에서, R1은 각각 독립적으로, 수소 원자(H), 불소 원자(F), 메틸기(-CH3), 탄소수 1 내지 20의 불소화 알킬기 또는 탄소수 1 내지 5의 히드록시알킬기이고, R2는 존재하지 않거나, 탄소수 1 내지 20의 알킬기이고, Z는 물에 대한 용해도를 증가시키기 위한 친수성 관능기이고, m 및 n은 상기 고분자를 구성하는 각 반복단위의 몰%로서, m은 10 내지 100몰%, n은 0 내지 90몰%이다.The cleaning solution composition of claim 1, wherein the water-soluble polymer is a polymer represented by the following Chemical Formula 2.
(2)
Figure pat00024

In Formula 2, R 1 is each independently a hydrogen atom (H), a fluorine atom (F), a methyl group (-CH 3 ), a fluorinated alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms, R 2 is absent or an alkyl group having 1 to 20 carbon atoms, Z is a hydrophilic functional group for increasing solubility in water, m and n are mole% of each repeating unit constituting the polymer, m is 10 to 100 Mol%, n is 0-90 mol%. 제4항에 있어서, 상기 Z는 히드록시기(-OH), 카르복실기(-COOH), 아민기(-NH2)로 이루어진 군으로부터 선택되는 친수성 작용기 또는 상기 친수성 작용기, 2차 및 3차 아민기(NH, N), 카보닐기(-CO-), 에스테르기(-COO-), 에테르기(-O-) 및 이들의 혼합물로 이루어진 군으로부터 선택되는 작용기를 포함하는 탄소수 1 내지 10의 사슬형, 분지형 또는 고리형 탄화수소기이다.The method of claim 4, wherein Z is a hydrophilic functional group selected from the group consisting of a hydroxyl group (-OH), a carboxyl group (-COOH), an amine group (-NH 2 ) or the hydrophilic functional group, secondary and tertiary amine groups (NH , N), carbonyl group (-CO-), ester group (-COO-), ether group (-O-) and a chain of 1 to 10 carbon atoms containing a functional group selected from the group consisting of Topographic or cyclic hydrocarbon groups. 제4항에 있어서, 상기 화학식 2로 표시되는 고분자는 하기 화학식 2a 내지 2h로 표시되는 고분자로 이루어진 군으로부터 선택되는 것인 세정액 조성물.
[화학식 2a]
Figure pat00025

[화학식 2b]
Figure pat00026

[화학식 2c]
Figure pat00027

[화학식 2d]
Figure pat00028

[화학식 2e]
Figure pat00029

[화학식 2f]
Figure pat00030

[화학식 2g]
Figure pat00031

[화학식 2h]
Figure pat00032

상기 화학식 2a 내지 2h에서, m 및 n은 상기 화학식 2에서 정의한 바와 같다.The cleaning liquid composition according to claim 4, wherein the polymer represented by Chemical Formula 2 is selected from the group consisting of a polymer represented by Chemical Formulas 2a to 2h.
(2a)
Figure pat00025

(2b)
Figure pat00026

[Formula 2c]
Figure pat00027

[Formula 2d]
Figure pat00028

[Formula 2e]
Figure pat00029

[Formula 2f]
Figure pat00030

[Formula 2g]
Figure pat00031

[Formula 2h]
Figure pat00032

In Formulas 2a to 2h, m and n are as defined in Formula 2.
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