KR20030050174A - Cleaning solution for photoresist - Google Patents

Cleaning solution for photoresist Download PDF

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KR20030050174A
KR20030050174A KR1020010080573A KR20010080573A KR20030050174A KR 20030050174 A KR20030050174 A KR 20030050174A KR 1020010080573 A KR1020010080573 A KR 1020010080573A KR 20010080573 A KR20010080573 A KR 20010080573A KR 20030050174 A KR20030050174 A KR 20030050174A
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photoresist
compound
group
cleaning liquid
liquid composition
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KR1020010080573A
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KR100733197B1 (en
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황영선
이근수
정재창
신기수
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주식회사 하이닉스반도체
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Priority to KR1020010080573A priority Critical patent/KR100733197B1/en
Priority to US10/317,578 priority patent/US7563753B2/en
Priority to CNB021518629A priority patent/CN1240816C/en
Publication of KR20030050174A publication Critical patent/KR20030050174A/en
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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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • 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
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

PURPOSE: Provided are a cleaning solution composition which is used for preventing the breakage of photoresist pattern, a method for forming a photoresist pattern by using the same, and a semiconductor device obtained by the method. CONSTITUTION: The composition comprises a compound of formula 1, an alcohol compound, and water. In the formula 1, each of R and R1 is hydrogen, C1-C10 alkyl, aryl, azine, aminoalkyl, aminoaryl, carboxylic acid group, or sulfonic acid group, R' is amino group, hydroxyl group, C1-C10 alkyl, aryl, azine, aminoalkyl, aminoaryl, carboxylic acid group, or sulfonic group, A is C1-C5 alkylene or C3-C10 aromatic ring, and n is an integer of 0-2. The ratio of the compound of formula 1: alcohol compound: water is 0.001-5:0.01-10:85-99.989(wt%).

Description

포토레지스트 세정액 조성물{Cleaning solution for photoresist}Photoresist cleaning liquid composition {Cleaning solution for photoresist}

본 발명은 포토레지스트 패턴 형성시, 현상 후 마지막 공정으로 반도체 기판을 세정하는데 사용하는 포토레지스트 세정액 조성물에 관한 것으로, 더욱 상세하게는 하기 화학식 1의 계면활성제를 포함하는 포토레지스트 세정액 조성물 및 이를 이용하여 패턴 붕괴를 방지할 수 있는 패턴을 형성하는 방법에 관한 것이다.The present invention relates to a photoresist cleaning liquid composition used to clean a semiconductor substrate in a final process after development when forming a photoresist pattern, and more particularly, a photoresist cleaning liquid composition comprising a surfactant of Formula 1 below and using the same The present invention relates to a method of forming a pattern capable of preventing a pattern collapse.

근래에 디바이스가 점점 미세화 되어감에 따라 포토레지스트 패턴의 아스펙트비 (aspect ratio; 포토레지스트 두께, 즉 형성된 패턴의 높이/선폭)가 높아지게 되는데, 그 결과 세정 공정시에 패턴이 붕괴하는 문제가 발생한다.In recent years, as the device becomes more and more finer, the aspect ratio (photoresist thickness, ie, the height / line width of the formed pattern) of the photoresist pattern becomes high. As a result, the pattern collapses during the cleaning process. do.

포토레지스트 패턴의 붕괴는 형성된 포토레지스트 패턴의 높이가 임계 높이를 넘었을 때 모세관력 (capillary force)이 포토레지스트 자체의 탄성력을 능가하게 되어 패턴이 쓰러지게 되는 것이다. 이를 해결하기 위하여 포토레지스트 내부의 탄성을 증가시키거나 포토레지스트 자체의 표면장력을 낮춰 피식각층과 포토레지스트 사이의 부착력을 높이는 방법 등을 시도할 수 있다.The collapse of the photoresist pattern is that when the height of the formed photoresist pattern exceeds the critical height, the capillary force exceeds the elastic force of the photoresist itself, causing the pattern to collapse. In order to solve this problem, a method of increasing the elasticity inside the photoresist or lowering the surface tension of the photoresist itself may increase the adhesion between the etched layer and the photoresist.

한편, 반도체 기판 상에 포토레지스트 패턴을 형성하는 일반적인 방법을 개략적으로 보면, 먼저 반도체 기판 상에 피식각층을 형성한 다음, 피식각층 위에 포토레지스트 막을 형성하고, 이를 노광 및 현상하여 상기 피식각층의 일부를 노출시키는 포토레지스트 패턴을 형성한다. 이때 포지티브형 포토레지스트 막을 사용한 경우에는 노광 영역의 포토레지스트 막이 현상액에 의해 제거되어 포토레지스트 패턴이 형성된다.Meanwhile, when a general method of forming a photoresist pattern on a semiconductor substrate is roughly described, first, an etching target layer is formed on a semiconductor substrate, and then a photoresist film is formed on the etching target layer, and the photoresist layer is exposed and developed to expose a portion of the etching target layer. A photoresist pattern is formed to expose the film. At this time, in the case of using a positive photoresist film, the photoresist film in the exposure area is removed by a developer to form a photoresist pattern.

상기와 같이 포토레지스트 패턴을 현상한 다음 마지막 공정으로 반도체 기판을 스핀시키면서 스핀 장치의 상부로부터 증류수를 분사시켜서 반도체 기판을 세정하는 과정을 거치는데, 이 과정에서 증류수의 표면장력이 높아 패턴이 붕괴하는 문제점이 발생한다.After developing the photoresist pattern as described above, the semiconductor substrate is cleaned by spraying distilled water from the top of the spin apparatus while spinning the semiconductor substrate. In this process, the surface tension of the distilled water is high so that the pattern collapses. A problem occurs.

이에 본 발명자들은 130nm 이하의 초미세 포토레지스트 패턴 형성시 현상공정에서 패턴이 붕괴되는 문제점을 해결하고자, 종래의 증류수 대신 표면장력을 낮춘 새로운 조성의 세정액을 사용함으로써 포토레지스트 패턴 붕괴를 방지할 수 있음을 알아내어 본 발명을 완성하였다.Accordingly, the present inventors can prevent the photoresist pattern collapse by using a cleaning solution of a new composition lowering the surface tension instead of distilled water in order to solve the problem that the pattern collapses in the development process when forming an ultra-fine photoresist pattern of less than 130nm. The present invention was completed by finding out.

본 발명의 목적은 포토레지스트 패턴의 붕괴를 방지할 목적으로 사용하는 새로운 조성의 세정액 조성물을 제공하는 것이다.An object of the present invention is to provide a cleaning liquid composition having a new composition for use for the purpose of preventing the collapse of the photoresist pattern.

또한 본 발명의 목적은 상기 세정액 조성물을 이용하여 포토레지스트 패턴을 형성하는 방법 및 이러한 방법에 의해 얻어진 반도체 소자를 제공하는 것이다.It is also an object of the present invention to provide a method of forming a photoresist pattern using the cleaning liquid composition and a semiconductor device obtained by such a method.

도 1은 본 발명에 따른 실시예 5에 의해 형성된 포토레지스트 패턴 사진.1 is a photoresist pattern photo formed by Example 5 according to the present invention.

도 2는 본 발명에 따른 실시예 6에 의해 형성된 포토레지스트 패턴 사진.Figure 2 is a photoresist pattern photo formed by Example 6 according to the present invention.

도 3은 본 발명에 따른 실시예 7에 의해 형성된 포토레지스트 패턴 사진.Figure 3 is a photoresist pattern photo formed by Example 7 according to the present invention.

도 4는 본 발명에 따른 실시예 8에 의해 형성된 포토레지스트 패턴 사진.Figure 4 is a photoresist pattern photo formed by Example 8 according to the present invention.

도 5는 비교예에 의해 형성된 포토레지스트 패턴 사진.5 is a photoresist pattern photo formed by the comparative example.

상기 목적을 달성하기 위하여 본 발명에서는 계면활성제로서 하기 화학식 1의 화합물을 포함하는 세정액 조성물을 제공한다.In order to achieve the above object, the present invention provides a cleaning liquid composition comprising a compound of formula 1 as a surfactant.

이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에서는 우선, 하기 화학식 1의 화합물, 알코올 화합물 및 물을 포함하는 포토레지스트 세정액 조성물을 제공한다.In the present invention, first, a photoresist cleaning liquid composition including a compound of Formula 1, an alcohol compound, and water is provided.

[화학식 1][Formula 1]

상기 식에서,Where

R 및 R'는 각각 수소, C1-C10의 알킬, 아릴, 아진, 아미노알킬, 아미노아릴, 카르복실산기 또는 술폰산기이고,R and R 'are each hydrogen, C 1 -C 10 alkyl, aryl, azine, aminoalkyl, aminoaryl, carboxylic acid groups or sulfonic acid groups,

R"는 아미노기, 히드록실기, C1-C10의 알킬, 아릴, 아진, 아미노알킬, 아미노아릴, 카르복실산기 또는 술폰산기이며,R ″ is an amino group, a hydroxyl group, a C 1 -C 10 alkyl, aryl, azine, aminoalkyl, aminoaryl, carboxylic acid group or sulfonic acid group,

상기 A는 C1-C5의 알킬렌 또는 C3-C10의 방향족 고리이고,A is C 1 -C 5 alkylene or C 3 -C 10 aromatic ring,

n은 0∼2 중에서 선택되는 정수이다.n is an integer selected from 0-2.

상기 세정액 조성물에서 계면활성제로 사용되는 화학식 1의 화합물은 물에 작 녹으며 수용액의 표면장력을 현저하게 저하시킴으로써 패턴 붕괴를 방지하는데 기여한다.The compound of Formula 1, which is used as a surfactant in the cleaning liquid composition, is slightly soluble in water and contributes to preventing pattern collapse by significantly lowering the surface tension of the aqueous solution.

상기 화학식 1의 화합물의 바람직한 예로는 술파아미드 (sulfamide), 술파디아진 (sulfadiazine), 술파닐 아미드 (sulfanil amide), 술파믹 산 (sulfamic acid) 술파닐 산 (sulfanilic acid) 또는 술파살라진 (sulfasalazine) 등을 들 수 있다. 상기 화합물들 중 술파닐 산을 제외한 화합물들은 모두 상기 화학식 1에서 n이 0인 경우의 술파아미드계 화합물이다.Preferred examples of the compound of Formula 1 include sulfamide, sulfadiazine, sulfanil amide, sulfamic acid sulfanilic acid or sulfasalazine ), And the like. All of the compounds except sulfanyl acid are sulfaamide compounds when n is 0 in Chemical Formula 1.

한편, 상기 알코올 화합물로는 C1-C10의 알킬 알코올 또는 알콕시알코올을 사용하는데, 바람직하게는 메탄올, 에탄올, 프로판올, 이소프로판올, n-부탄올, sec-부탄올, t-부탄올, 1-펜탄올, 2-펜탄올, 3-펜탄올 또는 2,2-디메틸-1-프로판올 등의 알킬 알코올을 사용하고, 2-메톡시에탄올, 2-(2-메톡시에톡시)에탄올, 1-메톡시-2-프로판 또는 3-메톡시-1,2-프로판디올 등의 알콕시알코올을 사용하며, 이들을 단독으로 또는 혼합하여 사용할 수 있다.Meanwhile, the alcohol compound may be a C 1 -C 10 alkyl alcohol or alkoxyalcohol, preferably methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, t-butanol, 1-pentanol, 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol, 1-methoxy-, using alkyl alcohols such as 2-pentanol, 3-pentanol or 2,2-dimethyl-1-propanol Alkoxy alcohols such as 2-propane or 3-methoxy-1,2-propanediol are used, and these may be used alone or in combination.

또한, 세정액 조성물의 물은 증류수를 사용한다.In addition, distilled water is used for the water of a washing | cleaning liquid composition.

상기 세정액 조성물에서, 화학식 1의 화합물 : 알코올 화합물 : 물의 조성비는 0.001∼5 중량% : 0.01∼10 중량% : 85∼99.989 중량%인 것이 바람직하다.In the cleaning liquid composition, the composition ratio of the compound of formula 1: alcohol compound: water is preferably 0.001 to 5% by weight: 0.01 to 10% by weight: 85 to 99.989% by weight.

본 발명에 따른 세정액 조성물은 상기 조성의 화학식 1의 화합물, 알코올 화합물 및 물의 혼합용액을 0.2㎛ 여과기로 여과함으로써 제조될 수 있다.The cleaning liquid composition according to the present invention may be prepared by filtering a mixed solution of the compound of Formula 1, an alcohol compound, and water with a 0.2 μm filter.

이러한 본 발명의 세정액 조성물은 현상액을 사용하는 즉, 습식현상 공정을 채택하는 포토레지스트 패턴 형성공정에 사용 가능하다.Such a cleaning liquid composition of the present invention can be used for a photoresist pattern forming process that uses a developer, that is, a wet development process.

본 발명에서는 또한 상기 세정액 조성물을 이용하는 포토레지스트 패턴 형성방법을 제공하는데, 그 과정은 하기와 같은 단계를 포함한다:The present invention also provides a method of forming a photoresist pattern using the cleaning liquid composition, the process comprising the following steps:

(a) 반도체 기판에 형성된 피식각층 상부에 통상의 포토레지스트를 도포하여 포토레지스트 막을 형성하는 단계;(a) forming a photoresist film by applying a conventional photoresist on the etched layer formed on the semiconductor substrate;

(b) 상기 포토레지스트 막을 노광원으로 노광하는 단계(b) exposing the photoresist film to an exposure source

(c) 상기 노광된 포토레지스트 막을 현상액으로 현상하는 단계; 및(c) developing the exposed photoresist film with a developer; And

(d) 상기 결과물을 본 발명에 따른 세정액 조성물로 세정하는 단계.(d) washing the resultant with the cleaning liquid composition according to the present invention.

상기 과정에서 (b)단계의 노광전에 소프트 베이크 공정, 또는 (b)단계의 노광후에 포스트 베이크 공정을 실시하는 단계를 더 포함할 수 있으며, 이 베이크 공정은 70 내지 200℃에서 수행되는 것이 바람직하다.The process may further include a soft bake process before the exposure of step (b), or a post bake process after the exposure of step (b), which is preferably carried out at 70 to 200 ℃. .

또한, 상기 노광공정은 VUV (157nm), ArF (193nm), KrF (248nm), EUV (13nm), E-빔, X-선 또는 이온빔을 노광원으로 사용하여, 0.1 내지 50mJ/cm2의 노광에너지로 수행되는 것이 바람직하다.In addition, the exposure step is exposed to 0.1 to 50mJ / cm 2 using VUV (157nm), ArF (193nm), KrF (248nm), EUV (13nm), E-beam, X-rays or ion beams as the exposure source It is preferably carried out with energy.

한편, 상기에서 현상 단계 (c)는 알칼리 현상액을 이용하여 수행될 수 있으며, 알칼리 현상액은 0.01 내지 5 중량%의 테트라메틸암모늄하이드록사이드(TMAH) 수용액인 것이 바람직하다.On the other hand, the developing step (c) in the above may be performed using an alkaline developer, the alkaline developer is preferably 0.01 to 5% by weight of tetramethylammonium hydroxide (TMAH) aqueous solution.

본 발명에서는 전술한 바와 같이, 현상의 마지막 단계에서 계면활성제인 화학식 1의 화합물을 포함하는 세정액 조성물로 세정하는 공정을 거침으로써, 세정액 조성물의 표면장력이 낮아지기 때문에 포토레지스트 패턴 형성시 현상공정에서 패턴이 붕괴되는 현상을 개선시킬 수 있다.In the present invention, as described above, the surface tension of the cleaning liquid composition is lowered by going through the process of cleaning with the cleaning liquid composition containing the compound of Formula 1, which is a surfactant at the last stage of development, so that the pattern in the developing process when the photoresist pattern is formed This collapse can be improved.

본 발명에서는 또한 상기 패턴 형성방법을 이용하여 제조된 반도체 소자를 제공한다.The present invention also provides a semiconductor device manufactured using the pattern forming method.

이하 본 발명을 실시예에 의하여 상세히 설명한다. 단 실시예는 발명을 예시하는 것일뿐 본 발명이 하기 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by examples. However, the examples are only to illustrate the invention and the present invention is not limited by the following examples.

실시예 1 : 본 발명에 따른 세정액 조성물 제조 (1)Example 1 Preparation of Cleaning Liquid Composition According to the Present Invention (1)

술파살라진 0.5g, 이소프로판올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.0.5 g of sulfasalazine, 4 g of isopropanol, and 95 g of water were stirred and mixed for 1 minute, and then filtered through a 0.2 μm filter to prepare a cleaning liquid composition according to the present invention.

실시예 2 : 본 발명에 따른 세정액 조성물 제조 (2)Example 2 Preparation of Washing Liquid Composition According to the Present Invention (2)

술파닐 산 0.5g, 에탄올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.0.5 g of sulfanyl acid, 4 g of ethanol, and 95 g of water were stirred and mixed for 1 minute, and then filtered through a 0.2 μm filter to prepare a cleaning liquid composition according to the present invention.

실시예 3 : 본 발명에 따른 세정액 조성물 제조 (3)Example 3 Preparation of Cleaning Liquid Compositions According to the Invention (3)

술파믹 산 0.5g, 이소프로판올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.0.5 g of sulfamic acid, 4 g of isopropanol, and 95 g of water were stirred and mixed for 1 minute, and then filtered through a 0.2 μm filter to prepare a cleaning liquid composition according to the present invention.

실시예 4 : 본 발명에 따른 세정액 조성물 제조 (4)Example 4 Preparation of Washing Liquid Composition According to the Present Invention (4)

술파닐 아미드 0.5g, 1-펜탄올 4g 및 물 95g을 1분간 교반하여 섞어준 후 이를 0.2㎛ 여과기로 여과하여 본 발명에 따른 세정액 조성물을 제조하였다.0.5 g of sulfanyl amide, 4 g of 1-pentanol and 95 g of water were stirred and mixed for 1 minute, and then filtered through a 0.2 μm filter to prepare a cleaning liquid composition according to the present invention.

실시예 5 : 포토레지스트 패턴 형성 (1)Example 5 Photoresist Pattern Formation (1)

헥사메틸디실라잔(HMDS) 처리된 실리콘 웨이퍼에 피식각층을 형성시키고, 그 상부에 메타크릴레이트 타입의 감광제인 Clariant사의 AX1020P를 3000rpm으로 스핀 코팅하여 포토레지스트 박막을 제조한 다음, 120℃의 오븐에서 90초간 소프트 베이크 하였다. 소프트 베이크 후 ArF 레이저 노광장비로 노광하고, 120℃의 오븐에서 90초간 다시 포스트 베이크 하였다. 베이크 완료후 2.38 중량% 테트라메틸암모늄하이드록사이드 수용액에 30초간 침지하여 현상 후, 실리콘 웨이퍼를 스핀시키면서 스핀 장치의 상부로부터 실시예 1에서 제조한 세정액 30㎖를 분사시켜 세정한 후, 이를 건조시켜 100㎚ L/S 초미세 포토레지스트 패턴을 얻었다 (도 1 참조).An etched layer was formed on a hexamethyldisilazane (HMDS) -treated silicon wafer, and a photoresist thin film was prepared by spin-coating a methacrylate-type photosensitive agent Clariant's AX1020P at 3000 rpm, followed by an oven at 120 ° C. Soft bake for 90 seconds at. After soft baking, it exposed with the ArF laser exposure equipment, and post-baked again for 90 second in 120 degreeC oven. After baking, the solution was immersed in an aqueous 2.38% by weight tetramethylammonium hydroxide solution for 30 seconds, and then developed. A 100 nm L / S ultrafine photoresist pattern was obtained (see FIG. 1).

실시예 6 : 포토레지스트 패턴 형성 (2)Example 6 Photoresist Pattern Formation (2)

실시예 2에서 제조한 세정액을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 100㎚ L/S 초미세 포토레지스트 패턴을 얻었다 (도 2 참조).A 100 nm L / S ultrafine photoresist pattern was obtained in the same manner as in Example 1 except that the cleaning solution prepared in Example 2 was used (see FIG. 2).

실시예 7 : 포토레지스트 패턴 형성 (3)Example 7 Photoresist Pattern Formation (3)

실시예 3에서 제조한 세정액을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 100㎚ L/S 초미세 포토레지스트 패턴을 얻었다 (도 3 참조).A 100 nm L / S ultrafine photoresist pattern was obtained in the same manner as in Example 1, except that the cleaning solution prepared in Example 3 was used (see FIG. 3).

실시예 8 : 포토레지스트 패턴 형성 (4)Example 8 Photoresist Pattern Formation (4)

실시예 4에서 제조한 세정액을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 100㎚ L/S 초미세 포토레지스트 패턴을 얻었다 (도 4 참조).A 100 nm L / S ultrafine photoresist pattern was obtained in the same manner as in Example 1 except that the cleaning solution prepared in Example 4 was used (see FIG. 4).

비교예 : 포토레지스트 패턴 형성 (5)Comparative Example: Forming Photoresist Pattern (5)

본 발명에 따른 세정액을 사용하는 대신 증류수를 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 포토레지스트 패턴을 얻었으나, 상기 실시예 5 내지 8에서 생성된 패턴과 달리 패턴이 붕괴되었다 (도 5 참조).A photoresist pattern was obtained in the same manner as in Example 1 except for using distilled water instead of using the cleaning solution according to the present invention, but unlike the patterns generated in Examples 5 to 8, the patterns collapsed (FIG. 5). Reference).

이상에서 살펴본 바와 같이, 화학식 1의 화합물, 알코올 화합물 및 물을 포함하는 본 발명의 세정액 조성물은 종래에 세정액으로 사용하던 증류수보다 표면장력이 낮기 때문에 포토레지스트 패턴 형성시, 현상 후 마지막 공정으로 반도체 기판을 세정하는데 사용하면 패턴 붕괴 현상이 크게 감소함을 알 수 있었다. 따라서 본 발명의 세정액 조성물은 130nm 이하의 초미세 포토레지스트 패턴 형성 공정의 안정화에 크게 기여할 것으로 보인다.As described above, since the cleaning liquid composition of the present invention comprising the compound of Formula 1, an alcohol compound, and water has a lower surface tension than distilled water, which is conventionally used as a cleaning liquid, the semiconductor substrate is the last step after the development of the photoresist pattern. It can be seen that the pattern collapse phenomenon is greatly reduced when used to clean the. Therefore, the cleaning liquid composition of the present invention is expected to contribute greatly to the stabilization of the ultrafine photoresist pattern formation process of 130nm or less.

Claims (9)

하기 화학식 1의 화합물, 알코올 화합물 및 물을 포함하는 것을 특징으로 하는 포토레지스트 세정액 조성물.A photoresist cleaning liquid composition comprising a compound of Formula 1, an alcohol compound, and water. [화학식 1][Formula 1] 상기 식에서,Where R 및 R'는 각각 수소, C1-C10의 알킬, 아릴, 아진, 아미노알킬, 아미노아릴, 카르복실산기 또는 술폰산기이고,R and R 'are each hydrogen, C 1 -C 10 alkyl, aryl, azine, aminoalkyl, aminoaryl, carboxylic acid groups or sulfonic acid groups, R"는 아미노기, 히드록실기, C1-C10의 알킬, 아릴, 아진, 아미노알킬, 아미노아릴, 카르복실산기 또는 술폰산기이며,R ″ is an amino group, a hydroxyl group, a C 1 -C 10 alkyl, aryl, azine, aminoalkyl, aminoaryl, carboxylic acid group or sulfonic acid group, 상기 A는 C1-C5의 알킬렌 또는 C3-C10의 방향족 고리이고,A is C 1 -C 5 alkylene or C 3 -C 10 aromatic ring, n은 0∼2 중에서 선택되는 정수이다.n is an integer selected from 0-2. 제 1 항에 있어서,The method of claim 1, 상기 화학식 1의 화합물 : 알코올 화합물 : 물의 비율은 0.001∼5 중량% : 0.01∼10 중량% : 85∼99.989 중량%인 것을 특징으로 하는 포토레지스트 세정액 조성물.The ratio of the compound of Formula 1: an alcohol compound: water is 0.001 to 5% by weight: 0.01 to 10% by weight: 85 to 99.989% by weight. 제 1 항에 있어서,The method of claim 1, 상기 화학식 1의 화합물은 술파아미드, 술파디아진, 술파닐 아미드, 술파믹 산, 술파닐 산 및 술파살라진 중에서 선택되는 것을 특징으로 하는 포토레지스트 세정액 조성물.The compound of Formula 1 is selected from sulfaamide, sulfadiazine, sulfanyl amide, sulfamic acid, sulfanyl acid and sulfasalazine. 제 1 항에 있어서,The method of claim 1, 상기 알코올 화합물은 C1-C10의 알킬 알코올 및 C1-C10의알콕시알코올로 이루어진 군으로부터 선택된 것을 단독으로 또는 혼합하여 사용하는 것을 특징으로 하는 포토레지스트 세정액 조성물.The alcohol compound is selected from the group consisting of C 1 -C 10 alkyl alcohol and C 1 -C 10 alkoxyalcohol, photoresist cleaning liquid composition, characterized in that used alone or in combination. 제 4 항에 있어서,The method of claim 4, wherein 상기 C1-C10의 알킬 알코올은 메탄올, 에탄올, 프로판올, 이소프로판올, n-부탄올, sec-부탄올, t-부탄올, 1-펜탄올, 2-펜탄올, 3-펜탄올 및 2,2-디메틸-1-프로판올로 이루어진 군으로부터 선택되고, 상기 C1-C10의 알콕시알코올은 2-메톡시에탄올, 2-(2-메톡시에톡시)에탄올, 1-메톡시-2-프로판올 및 3-메톡시-1,2-프로판디올로 이루어진 군으로부터 선택되는 것을 특징으로 하는 포토레지스트 세정액 조성물.The alkyl alcohol of C 1 -C 10 is methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol and 2,2-dimethyl -1-propanol, and the C 1 -C 10 alkoxyalcohol is 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol, 1-methoxy-2-propanol and 3- Photoresist cleaning liquid composition, characterized in that it is selected from the group consisting of methoxy-1,2-propanediol. (a) 반도체 기판에 형성된 피식각층 상부에 포토레지스트를 도포하여 포토레지스트 막을 형성하는 단계;(a) forming a photoresist film by applying a photoresist on the etched layer formed on the semiconductor substrate; (b) 상기 포토레지스트 막을 노광하는 단계;(b) exposing the photoresist film; (c) 상기 노광된 포토레지스트 막을 현상액으로 현상하는 단계; 및(c) developing the exposed photoresist film with a developer; And (d) 상기 결과물을 제 1 항 기재의 세정액 조성물로 세정하는 단계를 포함하는 것을 특징으로 하는 포토레지스트 패턴 형성방법.(d) washing the resultant with a cleaning liquid composition according to claim 1; 제 6 항에 있어서,The method of claim 6, 상기 (b)단계의 노광전에 소프트 베이크 공정 및 (b)단계의 노광후에 포스트 베이크 공정을 실시하는 단계를 더 포함하는 것을 특징으로 하는 포토레지스트 패턴 형성방법.And performing a soft bake process before the exposure of step (b) and a post bake process after the exposure of step (b). 제 6 항에 있어서,The method of claim 6, 상기 노광 단계의 노광원은 VUV, ArF, KrF, EUV, E-빔, X-선 및 이온빔으로 이루어진 군으로부터 선택된 것을 특징으로 하는 포토레지스트 패턴 형성방법.The exposure source of the exposure step is a photoresist pattern forming method, characterized in that selected from the group consisting of VUV, ArF, KrF, EUV, E-beam, X-ray and ion beam. 제 6 항 기재의 방법을 이용하여 제조된 반도체 소자.A semiconductor device manufactured using the method of claim 6.
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