KR20020049448A - Chemical rinse composition - Google Patents

Chemical rinse composition Download PDF

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KR20020049448A
KR20020049448A KR1020000078621A KR20000078621A KR20020049448A KR 20020049448 A KR20020049448 A KR 20020049448A KR 1020000078621 A KR1020000078621 A KR 1020000078621A KR 20000078621 A KR20000078621 A KR 20000078621A KR 20020049448 A KR20020049448 A KR 20020049448A
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hydroxide
rinse composition
chemical rinse
benzotriazole
cleaning
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KR1020000078621A
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KR100361481B1 (en
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오창일
이상대
유종순
윤석일
김성배
박순희
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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
    • G03F7/26—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
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/82—Auxiliary processes, e.g. cleaning or inspecting
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/6715—Apparatus for applying a liquid, a resin, an ink or the like

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

PURPOSE: A chemical rinse composition is provided to prevent the corrosion of a metal circuit pattern by finally removing a resist in a process of a TFT LCD device and a semiconductor device, and by rinsing stripper liquid remained. CONSTITUTION: The chemical rinse composition for rinsing a resist stripper comprises a) 0.05-3 wt.% of inorganic alkali or organic alkali represented by the formula(wherein R1-R4 are identical or different, and represents C1-4 alkyl group or C6-10 allyl group), b) 0.05-3 wt.% of at least one triazole-based anticorrosive agent, c) 0.1-30 wt.% of organic solvent, and d) 60-99 wt.% of water. The inorganic alkali is selected from a group consisting of potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, and a mixture thereof. The at least one triazole-based anticorrosive agent is selected from a group consisting of benzotriazole, tolyltriazole, carboxylic benzotriazole, 1-hydroxy benzotriazole(HBT), and nitro benzotriazole(NBT).

Description

케미칼 린스 조성물{CHEMICAL RINSE COMPOSITION}Chemical rinse composition {CHEMICAL RINSE COMPOSITION}

본 발명은 티에프티 엘시디 디바이스와 반도체 디바이스 제조 공정의 레지스트 스트리퍼 세정용 케미칼 린스 조성물에 관한 것으로, 보다 상세하게는 티에프티 엘시디 디바이스와 반도체 디바이스 제조 공정에서 레지스트를 최종 제거한 후 사용되고 남은 스트리퍼액을 세정하는 것을 주목적으로 하는 케미칼 린스 조성물에 관한 것이다.The present invention relates to a chemical rinse composition for cleaning a resist stripper in a TFT LCD device and a semiconductor device manufacturing process. More particularly, the present invention relates to cleaning a stripper liquid used after the final removal of a resist in a TFT LCD device and a semiconductor device manufacturing process. The present invention relates to a chemical rinse composition.

일반적으로 티에프티 엘시디 디바이스와 반도체 디바이스를 리소그래피법에 의해 제조하는 경우, 글라스, 실리콘 웨이퍼 등의 기판상에 알루미늄, 알루미늄 알로이, 구리 등의 금속막이나 산화막 등의 절연막을 형성한 후, 그 표면에 레지스트를 균일하게 도포하고, 이것을 노광 및 현상 처리하여 레지스트 패턴을 형성하며, 상기 레지스트 패턴을 마스크(mask)로 하여 하층부의 얇은 막을 선택적 에칭(etching)하여 패턴을 형성시킨 후, 불필요한 레지스트를 기판상에서 스트리퍼로 완전히 제거하는 일련의 공정이 진행된다.In general, when a TFT LCD device and a semiconductor device are manufactured by a lithography method, an insulating film such as an oxide film, a metal film such as aluminum, aluminum alloy, copper, or the like is formed on a substrate such as glass or a silicon wafer. The resist is uniformly applied, and the resist pattern is exposed and developed to form a resist pattern. The resist pattern is used as a mask to selectively form a thin film of an underlying layer to form a pattern, and then unnecessary resist is formed on the substrate. A series of processes are carried out with strippers completely removed.

상기 기판 상에서 레지스트를 제거하는 스트리퍼로는, 알킬벤젠술폰산을 주성분으로 하는 유기 술폰산계 스트리퍼, 모노에탄올아민 등의 유기아민을 주성분으로 하는 유기아민계 스트리퍼들이 공지되어 있다. 그러나 유기 술폰산계 스트리퍼는 작업시 안전성에 문제가 있어서, 근래에는 모노에탄올아민 등의 유기아민을 주성분으로 하는 유기아민계 스트리퍼가 주로 사용되고 있다.As strippers for removing the resist on the substrate, organic amine strippers having an organic amine such as alkyl benzene sulfonic acid as the main component and organic amines such as monoethanolamine are known. However, the organic sulfonic acid stripper has a problem in safety during operation, and in recent years, an organic amine stripper mainly containing organic amines such as monoethanolamine is mainly used.

이와 같이 유기아민계 스트리퍼로 레지스트 패턴층을 제거한 후 기판을 순수로 세정 처리하는 것이 일반적이나, 순수에 의한 세정 공정은 스트리퍼를 단시간 내에 완전히 세정하기 어렵고, 세정시간이 길어지면 금속막 및 절연막에 부식이 발생하기 때문에 순수로 세정하기 전에 스트리퍼를 케미칼 린스 조성물로 세정 처리한다.As such, it is common to clean the substrate with pure water after removing the resist pattern layer with an organic amine stripper. However, in the cleaning process with pure water, it is difficult to completely clean the stripper within a short time. Because of this, the stripper is washed with the chemical rinse composition before washing with pure water.

종래에 사용되는 린스 조성물로는 메탄올, 에탄올, 이소프로필알콜, 아세톤, 디메틸설폭사이드 (Dimethylsulfoxide) 등이 사용되고 있었으나, 상기 용매로서는 충분한 세정력을 기대할 수 없으며, 특히 미세회로 부위의 세정이 곤란하다. 또한 상기 용제는 인화성 또는 저장성에 문제점을 갖고 있기 때문에 취급시 각별한 주의를 요하므로 작업능률이 떨어지는 문제점이 있다.Methanol, ethanol, isopropyl alcohol, acetone, dimethyl sulfoxide (Dimethylsulfoxide) and the like have been used as a rinse composition conventionally used, but sufficient cleaning power cannot be expected as the solvent, and in particular, it is difficult to clean microcircuit sites. In addition, since the solvent has a problem in flammability or storage properties, there is a problem in that the work efficiency is lowered because special care is required during handling.

따라서, 우수한 세정력을 가짐과 동시에, 금속막질의 부식을 방지하고, 인화성 및 저장성에 있어 문제가 없는 스트리퍼 세정용 케미칼 린스 조성물이 요구되고 있다.Therefore, there is a need for a chemical rinse composition for stripper cleaning that has excellent cleaning power, prevents corrosion of metal film, and has no problem in flammability and shelf life.

본 발명은 상기 문제점을 해결하기 위해 안출된 것으로서, 본 발명자들은 유기 또는 무기 알칼리 및 트리아졸계 부식 방지제 등을 특정 비율로 함유하는 린스 조성물이 상기 요건을 충족시킬 수 있음을 발견하고 본 발명을 완성하기에 이르렀다.SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and the present inventors have found that a rinse composition containing an organic or inorganic alkali and a triazole-based corrosion inhibitor and the like in a specific ratio can satisfy the above requirements and complete the present invention. Reached.

따라서, 본 발명은 인화점이 높거나 없으며, 저장에 문제가 없으며, 금속막질의 부식을 방지하고, 린스 효과가 높은 티에프티 엘시디 디바이스와 반도체 디바이스 스트리퍼 세정용 케미칼 린스 조성물을 제공함을 그 목적으로 한다.Accordingly, an object of the present invention is to provide a chemical rinse composition for cleaning a TFT device and a semiconductor device stripper having high flash point, no storage problem, preventing corrosion of metal film, and high rinsing effect.

상기 목적을 달성하기 위해서, 본 발명은 레지스트 스트리퍼 세정용 케미칼 린스 조성물에 있어서,In order to achieve the above object, the present invention provides a chemical rinse composition for resist stripper cleaning,

a) 무기 알칼리 또는 유기 알칼리 0.05 ~ 3 중량%;a) 0.05 to 3 weight percent of an inorganic alkali or an organic alkali;

b) 하나 이상의 트리아졸계 부식방지제 0.05 ~ 3 중량%;b) 0.05 to 3 weight percent of one or more triazole-based preservatives;

c) 유기용제 0.1 ~ 30 중량%; 및c) 0.1 to 30% by weight of an organic solvent; And

d) 물 60 ~ 99 중량%d) 60 to 99% by weight of water

를 포함하는 것을 특징으로 하는 레지스트 스트리퍼 세정용 케미칼 린스 서를 제공한다.It provides a chemical rinse stand for cleaning the resist stripper comprising a.

본 발명의 레지스트 스트리퍼 세정용 케미칼 린스 조성물에 있어서, 상기 a) 성분으로서, 수산화칼륨, 수산화나트륨, 인산나트륨, 규산나트륨 등의 무기 알칼리나, 테트라메틸암모늄 하이드록사이드, 트리메틸(2-하이드록시에틸)암모늄 하이드록사이드 등의 유기 알칼리가 단독 또는 혼합으로 사용된다.In the chemical rinse composition for cleaning a resist stripper of the present invention, as the component a), an inorganic alkali such as potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, tetramethylammonium hydroxide, trimethyl (2-hydroxyethyl Organic alkalis, such as ammonium hydroxide, are used individually or in mixture.

이중 유기 알칼리는 화학식 1Double organic alkali is of formula 1

(R1-R4는 동일하거나 다를 수 있으며, 탄소수 1-4의 알킬기 또는 탄소수 6-10의 아릴기를 나타낸다)로 표시되며, 테트라메틸암모늄 하이드록사이드, 테트라에틸암모늄 하이드록사이드, 테트라프로필암모늄 하이드록사이드, 테트라부틸암모늄 하이드록사이드, 트리메틸에틸암모늄 하이드록사이드, 디메틸디에틸암모늄 하이드록사이드, 트리메틸(2-하이드록시에틸)암모늄 하이드록사이드, 트리에틸(2-하이드록시에틸)암모늄 하이드록사이드, 트리프로필(2-하이드록시에틸)암모늄 하이드록사이드, 트리메틸(1-하이드록시프로필)암모늄 하이드록사이드, 트리부틸(2-하이드록시에틸)암모늄 하이드록사이드 등을 사용할 수 있다.(R 1 -R 4 may be the same or different, and represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms), and tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, dimethyldiethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, triethyl (2-hydroxyethyl) ammonium hydride The hydroxide, tripropyl (2-hydroxyethyl) ammonium hydroxide, trimethyl (1-hydroxypropyl) ammonium hydroxide, tributyl (2-hydroxyethyl) ammonium hydroxide and the like can be used.

상기 린스 공정이 잔류 금속에 큰 영향을 받지 않는 디바이스 제조공정일 경우에는 수산화칼륨 (KOH) 등의 무기 알칼리가 사용 가능하다.In the case where the rinse process is a device manufacturing process that is not greatly influenced by residual metal, inorganic alkali such as potassium hydroxide (KOH) may be used.

상기 a) 성분의 함량은 0.05 ~ 3 중량%가 바람직하다. 상기 성분의 함량이 0.05 중량% 미만이면 레지스트의 고분자 성분으로의 침투력이 약화되어 린스 조성물의 세정 속도가 늦어지며, 3 중량%를 초과하면 알루미늄(Al) 등의 금속막질의 부식현상이 심해지는 문제점이 발생한다.The content of component a) is preferably 0.05 to 3% by weight. When the content of the component is less than 0.05% by weight, the penetration of the resist into the polymer component is weakened, so that the rinsing speed of the rinse composition is slowed. When the content of the component is more than 3% by weight, the corrosion of metal film such as aluminum (Al) is severe. This happens.

본 발명의 레지스트 스트리퍼 세정용 케미칼 린스 조성물에 있어서, b) 트리아졸계 부식방지제로서, 벤조트리아졸(Benzotriazole), 톨리트리아졸(Tolytriazole), 카르복실릭 벤조트리아졸(Carboxylicbenzotriazole), 1-하이드록시 벤조트리아졸(HBT), 니트로 벤조트리아졸(NBT) 등이 사용될 수 있으며, 이들은 상온에서 고체 상태로 존재하고 물에 용해되기 어렵기 때문에 미리 유기 용제에 녹여 액상으로 제조한 후 사용하는 것이 좋다. 트리아졸 계의 부식방지제는 트리아졸 분자와 금속표면에 강한 결합이 형성되는 화학흡착(chemisorption)을 이루게 되어, 금속부식의 원인인 유기아민 성분의 침투를 막아주어 부식방지 효과를 나타내게 된다.In the chemical rinse composition for cleaning the resist stripper of the present invention, b) as a triazole-based corrosion inhibitor, benzotriazole, tolytriazole, carboxylic benzotriazole, 1-hydroxy Benzotriazole (HBT), nitro benzotriazole (NBT) and the like may be used, and since they exist in a solid state at room temperature and are difficult to dissolve in water, it is preferable to dissolve them in an organic solvent in advance to prepare them in a liquid state. The triazole type corrosion inhibitor forms a chemisorption that forms strong bonds with the triazole molecule and the metal surface, thereby preventing the penetration of the organic amine component, which causes metal corrosion, and exhibits an anticorrosion effect.

상기 트리아졸계 부식방지제의 함량은 0.05 내지 3 중량%가 바람직하다. 트리아졸계 부식방지제의 함량이 0.05 중량% 미만이면 금속막질층이 부식되는 문제점이 있고, 3 중량%를 초과하면 세정 공정시 거품이 형성되어 공정 진행이 어렵다.The content of the triazole-based corrosion inhibitor is preferably 0.05 to 3% by weight. When the content of the triazole-based corrosion inhibitor is less than 0.05% by weight, there is a problem in that the metal film layer is corroded. When the content of the triazole-based corrosion inhibitor is more than 3% by weight, bubbles are formed during the cleaning process, making the process difficult.

본 발명의 레지스트 스트리퍼 세정용 케미칼 린스 조성물에 있어서, c) 유기용제로서, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노부틸에테르, 디메틸포름아마이드 (DMF), N-메틸포름아마이드, 디메틸아세트아마이드 (DMAc), N-메틸아세트아마이드, 디에틸아세트아마이드 (DEAc), N-메틸 피롤리돈 (NMP), N-에틸 피롤리돈 (NEP), N-프로틸 피롤리돈 (NPP), N-하이드록시메틸 피롤리돈, N-하이드록시에틸 피롤리돈 등이 하나 이상 사용될 수 있으며, 그 함량은 0.1 ~ 30 중량%가 바람직하다. 상기 유기용제들은 물과 잘 혼용될 수 있어야 하며, 레지스트 및 유기아민계 화합물을 충분히 용해할 수 있는 것이 바람직하다. 상기 유기 용제의 함량이 0.1 중량% 미만이면 레지스트 및 유기아민계 화합물에 대한 용해력이 떨어지며, 30 중량%를 초과하면 폐액 처리가 쉽지 않은 문제점이 있다.In the chemical rinse composition for cleaning a resist stripper of the present invention, c) as an organic solvent, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dimethylformamide (DMF), N-methyl Formamide, dimethylacetamide (DMAc), N-methylacetamide, diethylacetamide (DEAc), N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP), N-propyl pyrrolidone Don (NPP), N-hydroxymethyl pyrrolidone, N-hydroxyethyl pyrrolidone and the like may be used, and the content thereof is preferably 0.1 to 30% by weight. The organic solvents should be well mixed with water, it is preferable that the organic solvent and the organic amine-based compound can be sufficiently dissolved. If the content of the organic solvent is less than 0.1% by weight, the dissolving power of the resist and the organic amine-based compound is lowered, and if the content of more than 30% by weight, there is a problem that the waste liquid treatment is not easy.

본 발명의 레지스트 스트리퍼 세정용 케미칼 린스 조성물에 있어서, 필수 구성 성분인 d) 물은 이온교환수지를 통해 여과한 순수가 바람직한데, 비저항이 18메가오옴(㏁) 이상인 초순수를 사용하는 것이 더욱 바람직하다.In the resist stripper cleaning chemical rinse composition of the present invention, pure water filtered through an ion exchange resin is preferably d) water, which is an essential component, and more preferably, ultrapure water having a specific resistance of 18 megaohms or more is used. .

상기 물의 함량은 60 ∼ 99 중량%가 바람직하다. 본 발명에 따른 레지스트 스트리퍼 세정용 케미칼 린스 조성물중 물의 함량이 60 중량% 미만이면 폐액처리 등에 문제가 있으며, 물의 함량이 99 중량%를 초과되면 세정력이 떨어지는 문제점이 있다. 연구결과 물의 함량은 60 ~ 99 중량% 범위가 가장 바람직한 것으로 확인되었다.The water content is preferably 60 to 99% by weight. If the content of water in the resist stripper cleaning chemical rinse composition according to the present invention is less than 60% by weight, there is a problem such as waste liquid treatment, there is a problem that the cleaning power is lowered when the content of water exceeds 99% by weight. As a result, the water content was found to be the most preferable 60 ~ 99% by weight.

이하, 본 발명을 실시예를 통해 더욱 상세히 설명하고자 하는데, 본 발명의 범위가 하기 실시예로 한정되는 것이 아님은 물론이다. 한편, 하기 실시예에 있어서 별도의 언급이 없으면 백분율 및 혼합비는 중량을 기준으로 한 것이다. 본 발명의 실시예 및 비교예에 있어서, 레지스트 스트리퍼 세정용 케미칼 린스 조성물에 대한 성능평가는 다음 방법에 의하여 실시하였다. 세정력 평가는 접촉각 측정 (기판의 오염물질이 대부분 유기물질이므로 기판을 친수성으로 바꾸면 오염물이 쉽게 제거됨)과 강제오염 방법을 시행하였으며, 금속막 부식 시험을 시행하였다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples. On the other hand, in the following examples, unless otherwise stated, percentages and mixing ratios are based on weight. In Examples and Comparative Examples of the present invention, the performance evaluation of the chemical rinse composition for resist stripper cleaning was performed by the following method. The cleaning power was evaluated by contact angle measurement (contamination is easily removed when the substrate is changed to hydrophilic because most of the substrate is contaminant organic matter) and forced contamination method, and the metal film corrosion test.

[실시예]EXAMPLE

시편 제조Specimen Manufacturing

하부에 알루미늄이 증착되어 있는 LCD 글라스(Glass)에 범용적으로 사용되는 포지티브 포토레지스트(Positive photoresist) 조성물 (동진쎄미켐 사제, 상품명: DTFR-3650B)을 스핀 코팅하여 최종 막 두께가 3㎛가 되도록 도포한 후, 노광하여 2.38% 테트라메틸암모늄하이드록사이드 현상액으로 21℃에서 60초 현상하고, 120℃로 5분간 포스트 베이크(post bake)하여 패턴을 형성하였다.The positive photoresist composition (Dongjin Semichem Co., Ltd., product name: DTFR-3650B), which is generally used for LCD glass on which aluminum is deposited, is spin-coated to apply a final film thickness of 3 μm. After exposure, the resultant was developed for 60 seconds at 21 ° C. with a 2.38% tetramethylammonium hydroxide developer and post-baked at 120 ° C. for 5 minutes to form a pattern.

이어서, 알루미늄을 에칭(etchinig) 처리하여 회로 패턴을 형성한 후, 범용적인 포지티브용 스트리퍼 조성물 (동진쎄미켐 사제, 상품명: DPS-1000N)으로 레지스트 패턴을 박리하였다.Subsequently, aluminum was etched to form a circuit pattern, and then the resist pattern was peeled off with a general-purpose positive stripper composition (manufactured by Dongjin Semichem, trade name: DPS-1000N).

케미칼 린스 조성물의 제조Preparation of Chemical Rinse Composition

성분 a) - d)의 함량을 각각 하기 표 1에 나타낸 비율로 혼합하여 각각 실시예 1 ~ 6 및 비교예 1 ~ 4 의 케미칼 린스 조성물을 제조하였다.The chemical rinse compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared by respectively mixing the contents of the components a) to d) in the ratios shown in Table 1 below.

케미칼 린스 조성물의 조성(중량%)Composition (wt%) of chemical rinse composition (a) 알카리(a) alkali (b)트리아졸계 부식방지제(b) Triazole type corrosion inhibitor (c)유기용제(c) organic solvent (d)물(d) water 양amount 종류Kinds 양amount 종 류Kinds 양amount 종류Kinds 양amount 양amount 실시예Example 1One TMAH 0.5TMAH 0.5 BTBT 1.21.2 TTTT 0.30.3 DMAcDMAc 1313 8585 22 TMHEH 0.3TMHEH 0.3 BTBT 0.70.7 TTTT 0.30.3 DBEDBE 1.71.7 9797 33 TMAH 0.5TMAH 0.5 BTBT 0.50.5 TTTT 0.20.2 DMAcDMAc 0.80.8 9898 44 TMHEH 1.5TMHEH 1.5 BTBT 2.52.5 CBTCBT 2.52.5 NMPNMP 8.58.5 8585 55 KOH 1.5KOH 1.5 BTBT 33 TTTT 22 DEEDEE 13.513.5 8080 66 TMAH 0.2TMAH 0.2 BTBT 0.70.7 CBTCBT 0.10.1 DBEDBE 2929 7070 비교예Comparative example 1One TMAH 2.38TMAH 2.38 97.6297.62 22 DMSODMSO 100100 33 IPAIPA 100100 44 TMAH 0.5TMAH 0.5 DMSODMSO 3030 69.569.5

TMAH : 테트라메틸암모늄 하이드록사이드TMAH: Tetramethylammonium Hydroxide

TMHEH : 트리메틸(2-하이드록시에틸)암모늄 하이드록사이드TMHEH: Trimethyl (2-hydroxyethyl) ammonium hydroxide

DBE : 디에틸렌글리콜 모노부틸 에테르DBE: Diethylene Glycol Monobutyl Ether

DEE : 디에틸렌글리콜 모노에틸 에테르DEE: diethylene glycol monoethyl ether

DMAc : 디메틸아세트아마이드 (Dimethylacetamide)DMAc: Dimethylacetamide

NMP : N-메틸-2-피롤리돈NMP: N-methyl-2-pyrrolidone

BT : 벤조트리아졸 (Benzotriazole)BT: Benzotriazole

TT : 톨리트리아졸 (Tolytriazole)TT: Tolytriazole

CBT : 카르복실릭 벤조트리아졸 (Carboxylicbenzotriazole)CBT: Carboxylicbenzotriazole

이와 같이 하여 얻은 케미칼 린스 조성물에 대하여 상기에서 설명한 (1) 케미칼 린스 조성물 세정력 평가 시험, (2) 금속막질 부식성 시험을 실시하고 그 결과를 하기의 표 2 ~ 3 에 나타냈다.The thus obtained chemical rinse composition was subjected to the above-described (1) chemical rinse composition cleaning power evaluation test and (2) metal film corrosiveness test, and the results are shown in Tables 2 to 3 below.

케미칼 린스 조성물 세정력 평가 시험Chemical Rinse Composition Detergency Evaluation Test

A) 접촉각 측정A) Contact angle measurement

LCD용 글래스 (Glass)와 Al/Nd 시편, SiNx 시편을 70℃에서 스트리퍼액에 2분간 침지 시킨 후, 상온의 케미칼 린스 조성물에 1분간 침지시켰다. 계속하여, 상기 시편을 케미칼 린스 조성물로부터 꺼낸 후, 초순수로 수세하고 질소가스로 건조한 후, 접촉각 측정기(KRUSS사, 모델:G2)로 접촉각을 측정하여 시편의 표면 성질 변화 정도를 확인하였다. 이를 통한 린스 조성물의 상기 막질의 표면 개질 성능을 측정하였고 그 결과를 하기 표 2에 나타냈다.Glass, Al / Nd and SiNx specimens for LCD were immersed in a stripper solution at 70 ° C. for 2 minutes, and then immersed in a chemical rinse composition at room temperature for 1 minute. Subsequently, the specimen was removed from the chemical rinse composition, washed with ultrapure water and dried with nitrogen gas, and then the contact angle was measured with a contact angle measuring instrument (KRUSS, Model: G2) to determine the degree of change in the surface properties of the specimen. The surface modification performance of the film of the rinse composition through this was measured and the results are shown in Table 2 below.

B) 강제오염 세정력 측정B) Forced contamination cleaning power measurement

LCD용 글래스 (Glass)에 지문과 먼지와 스트리퍼 폐액으로 강제오염 시킨 후 케미칼 린스 조성물에 5분간 침지시킨 후 광학전자현미경(LEICA사, 모델:FTM-200)으로 측정하였고 그 결과를 하기 표 3에 나타냈다.The glass for LCD was forcibly contaminated with fingerprints, dust, and stripper waste solution, and then immersed in the chemical rinse composition for 5 minutes, and then measured by an optical electron microscope (LEICA, Model: FTM-200). The results are shown in Table 3 below. Indicated.

시험 막질Test membrane LCD 베어글래스(bare glass)LCD bare glass Al/NdAl / Nd SiNxSiNx 실시예Example 1One 20.1220.12 25.8325.83 60.1360.13 22 21.2221.22 24.5324.53 59.2159.21 33 20.0220.02 26.0126.01 61.2161.21 44 24.2124.21 24.2224.22 59.8859.88 55 23.2223.22 22.0122.01 60.7560.75 66 22.5122.51 24.1824.18 61.4161.41 비교예Comparative example 1One 34.5134.51 42.5142.51 76.1476.14 22 28.4228.42 30.5430.54 68.5268.52 33 27.2427.24 31.1531.15 65.4165.41 44 21.4121.41 28.8628.86 63.5863.58

오염 물질pollutant 먼지dust 지문Fingerprint 스트리퍼 폐액Stripper waste 실시예Example 1One 양호Good 양호Good 양호Good 22 양호Good 양호Good 양호Good 33 양호Good 양호Good 양호Good 44 양호Good 양호Good 양호Good 55 양호Good 양호Good 양호Good 66 양호Good 양호Good 양호Good 비교예Comparative example 1One 불량Bad 불량Bad 불량Bad 22 양호Good 양호Good 양호Good 33 불량Bad 불량Bad 불량Bad 44 양호Good 양호Good 양호Good

린스액 금속막질 부식성 시험Rinse Liquid Metal Film Corrosion Test

시편을 상온에서 케미칼 린스 조성물에 30분간 침지시켰다. 계속하여, 상기 시편을 케미칼 린스 조성물로부터 꺼낸 후, 초순수로 수세하고 질소가스로 건조한 후, 알루미늄 패턴 내에 부식이 발생했는지 여부를 주사전자현미경(SEM)으로 검사하였다. 케미칼 린스 조성물의 금속막질 부식방지 성능을 다음과 같은 기준에 의거하여 평가하고 그 결과를 하기 표 4에 나타냈다.The specimen was immersed in the chemical rinse composition for 30 minutes at room temperature. Subsequently, the specimen was removed from the chemical rinse composition, washed with ultrapure water and dried with nitrogen gas, and then examined by scanning electron microscopy (SEM) to see if corrosion occurred in the aluminum pattern. The metal film corrosion protection performance of the chemical rinse composition was evaluated based on the following criteria and the results are shown in Table 4 below.

O : 금속막질에 금속부식 현상이 없는 경우O: No metal corrosion on metal film

△ : 금속막질에 금속부식 현상이 일부 있는 경우(Triangle | delta): When the metal film has some metal corrosion phenomenon

× : 금속막질에 금속부식 현상이 심하게 나타난 경우×: When metal corrosion phenomenon is severely seen in the metal film

침지 시간Immersion time 30 분30 minutes 실시예Example 1One OO 22 OO 33 OO 44 OO 55 OO 66 OO 비교예Comparative example 1One XX 22 XX 33 XX 44 XX

상기한 바와 같이, 본 발명에 따른 케미칼 린스 조성물은 종래에 사용되던 메탄올, 에탄올, 이소프로필알콜, 아세톤, 디메틸설폭사이드 등의 유기 용제의 불완전한 세정성, 공정처리시간의 장기화, 인화성, 저장성 등의 문제점을 해결하여 특히 미세회로 부위의 세정이 가능하며, 인화점이 높거나 없으며, 저장안정성이 뛰어나고, 금속회로 패턴의 부식을 방지하며, 짧은 처리시간에도 불구하고 린스 효과가 높다는 장점을 가지고 있다.As described above, the chemical rinse composition according to the present invention includes incomplete cleaning of organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, dimethyl sulfoxide, prolonged processing time, flammability, shelf life, and the like. In particular, it is possible to clean the microcircuit area by solving the problem, has a high or no flash point, has excellent storage stability, prevents corrosion of the metal circuit pattern, and has a high rinsing effect despite a short treatment time.

Claims (6)

a) 무기 알칼리 또는 유기 알칼리 0.05 ~ 3 중량%;a) 0.05 to 3 weight percent of an inorganic alkali or an organic alkali; b) 하나 이상의 트리아졸계 부식방지제 0.05 ~ 3 중량%;b) 0.05 to 3 weight percent of one or more triazole-based preservatives; c) 유기용제 0.1 ~ 30 중량%; 및c) 0.1 to 30% by weight of an organic solvent; And d) 물 60 ~ 99 중량%d) 60 to 99% by weight of water 를 포함하는 것을 특징으로 하는 레지스트 스트리퍼 세정용 케미칼 린스 조성물.A chemical rinse composition for cleaning a resist stripper comprising a. 제 1항에 있어서, 상기 무기 알칼리는 수산화칼륨, 수산화나트륨, 인산나트륨, 규산나트륨 및 이들의 혼합물로 구성되는 군으로부터 선택되는 화합물인 것을 특징으로 하는 레지스트 스트리퍼 세정용 케미칼 린스 조성물.The chemical rinse composition of claim 1, wherein the inorganic alkali is a compound selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate and mixtures thereof. 제 1항에 있어서, 상기 유기 알카리는 화학식 1The method of claim 1, wherein the organic alkali is formula (1) [화학식 1][Formula 1] (R1-R4는 동일하거나 다를 수 있고 탄소수 1-4의 알킬기 또는 탄소수 6-10의아릴기를 나타낸다)로 표시되며, 테트라메틸암모늄 하이드록사이드, 테트라에틸암모늄 하이드록사이드, 테트라프로필암모늄 하이드록사이드, 테트라부틸암모늄 하이드록사이드, 트리메틸에틸암모늄 하이드록사이드, 디메틸디에틸암모늄 하이드록사이드, 트리메틸(2-하이드록시에틸)암모늄 하이드록사이드, 트리에틸(2-하이드록시에틸)암모늄 하이드록사이드, 트리프로필(2-하이드록시에틸)암모늄 하이드록사이드, 트리메틸(1-하이드록시프로필)암모늄 하이드록사이드, 트리부틸(2-하이드록시에틸)암모늄 하이드록사이드 및 이들의 혼합물로 구성되는 군 중에서 선택되는 화합물인 것을 특징으로 하는 레지스트 스트리퍼 세정용 케미칼 린스 조성물.(R 1 -R 4 may be the same or different and represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms), and tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide Hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, dimethyldiethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, triethyl (2-hydroxyethyl) ammonium hydroxide The group consisting of sides, tripropyl (2-hydroxyethyl) ammonium hydroxide, trimethyl (1-hydroxypropyl) ammonium hydroxide, tributyl (2-hydroxyethyl) ammonium hydroxide and mixtures thereof A chemical rinse composition for cleaning a resist stripper, characterized in that the compound is selected from. 제 1항에 있어서, 상기 트리아졸 계열의 부식방지제는 벤조트리아졸, 톨리트리아졸, 카르복실릭벤조트리아졸, 1-하이드록시 벤조트리아졸(HBT), 니트로 벤조트리아졸(NBT) 중에서 선택된 하나 이상의 화합물인 것을 특징으로 하는 레지스트 스트리퍼 세정용 케미칼 린스 조성물.According to claim 1, wherein the triazole-based corrosion inhibitor is selected from benzotriazole, tolytriazole, carboxylic benzotriazole, 1-hydroxy benzotriazole (HBT), nitro benzotriazole (NBT) A chemical rinse composition for cleaning a resist stripper, characterized in that at least one compound. 제 1항에 있어서, 상기 유기용제는 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노부틸에테르, 디메틸포름아마이드 (DMF), N-메틸포름아마이드, 디메틸아세트아마이드 (DMAc), N-메틸아세트아마이드, 디에틸아세트아마이드 (DEAc), N-메틸 피롤리돈 (NMP), N-에틸 피롤리돈 (NEP), N-프로틸 피롤리돈 (NPP), N-하이드록시메틸 피롤리돈, N-하이드록시에틸 피롤리돈 및 이들의 혼합물로 구성되는 군으로부터 선택되는 것을 특징으로 하는 레지스트 스트리퍼세정용 케미칼 린스 조성물.The organic solvent of claim 1, wherein the organic solvent is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dimethylformamide (DMF), N-methylformamide, and dimethylacetamide (DMAc). , N-methylacetamide, diethylacetamide (DEAc), N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP), N-propyl pyrrolidone (NPP), N-hydroxy A chemical rinse composition for cleaning a resist stripper, which is selected from the group consisting of methyl pyrrolidone, N-hydroxyethyl pyrrolidone and mixtures thereof. 제 1항에 있어서, 상기 물은 비저항 18 메가오옴(MΩ) 이상의 초순수인 것을 특징으로 하는 레지스트 스트리퍼 세정용 케미칼 린스 조성물.The chemical rinse composition of claim 1, wherein the water is ultrapure water having a resistivity of 18 megaohms (MΩ) or more.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100485737B1 (en) * 2001-11-27 2005-04-27 주식회사 동진쎄미켐 Thinner composition for removing resist
US7897325B2 (en) * 2004-12-09 2011-03-01 Tokyo Ohka Kogyo Co., Ltd. Lithographic rinse solution and method for forming patterned resist layer using the same
KR20140012309A (en) 2012-07-19 2014-02-03 동우 화인켐 주식회사 A composition for removing organic-inorganic hybrid alignment layer
KR20170088048A (en) * 2016-01-22 2017-08-01 주식회사 이엔에프테크놀로지 Photoresist stripper composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100485737B1 (en) * 2001-11-27 2005-04-27 주식회사 동진쎄미켐 Thinner composition for removing resist
US7897325B2 (en) * 2004-12-09 2011-03-01 Tokyo Ohka Kogyo Co., Ltd. Lithographic rinse solution and method for forming patterned resist layer using the same
KR20140012309A (en) 2012-07-19 2014-02-03 동우 화인켐 주식회사 A composition for removing organic-inorganic hybrid alignment layer
KR20170088048A (en) * 2016-01-22 2017-08-01 주식회사 이엔에프테크놀로지 Photoresist stripper composition

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