KR20020036117A - A composition for protection film having acid resistance - Google Patents
A composition for protection film having acid resistance Download PDFInfo
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- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
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- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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Abstract
Description
본 발명은 반도체 집적 회로의 미세 회로 제조에 사용되는 감광성 보호막 조성물에 관한 것이다. 보다 상세하게는 보호막을 형성하기 위한 성분으로 고분자 수지, 감광성 화합물 및 유기 용매를 포함하는 감광성 보호막 조성물에 관한 것이다.The present invention relates to a photosensitive protective film composition for use in the manufacture of fine circuits in semiconductor integrated circuits. More specifically, the present invention relates to a photosensitive protective film composition comprising a polymer resin, a photosensitive compound, and an organic solvent as a component for forming a protective film.
일반적으로 반도체 디바이스의 제조 공정은 반도체 기판 상에 형성된 도전층 위에 레지스트 패턴을 형성한 후 상기 패턴을 마스크로서 이용하여 상기 패턴에 의하여 덮이지 않은 부위의 도전층을 에칭하여 제거함으로써 도전층 패턴을 형성하는 리소그래피 공정을 수십 회 사용하게 된다. 상기 마스크로서 이용된 레지스트 패턴은 상기 도전층 패턴 형성 공정 이후의 스트립 공정에서 레지스트 리무버에 의하여도전층 위에서 제거되어야 한다. 그러나, 최근 초고집적회로 반도체 제조공정에 있어서는 도전층 패턴을 형성하기 위한 에칭 공정이 주로 건식(dry) 에칭 공정으로 이루어지기 때문에 이후의 스트립 공정에서 레지스트를 제거하는 것이 어렵다.In general, a semiconductor device manufacturing process is performed by forming a resist pattern on a conductive layer formed on a semiconductor substrate, and then forming a conductive layer pattern by etching the conductive layer in a portion not covered by the pattern by using the pattern as a mask. The lithography process uses dozens of times. The resist pattern used as the mask should be removed on the conductive layer by a resist remover in the strip process after the conductive layer pattern forming process. However, in the recent ultra-high integrated circuit semiconductor manufacturing process, since the etching process for forming the conductive layer pattern mainly consists of a dry etching process, it is difficult to remove the resist in a subsequent strip process.
건식 에칭 공정은 혼산의 액상 조성물을 이용하는 습식(wet) 에칭 공정을 대체하는 것으로서 플라즈마 에칭 가스와 도전층과 같은 물질막 사이의 기상-고상 반응을 이용하여 에칭 공정을 수행한다. 건식 에칭은 제어가 용이하고 샤프한 패턴을 얻을 수 있어 최근 에칭 공정의 주류를 이루고 있다. 그러나, 건식 에칭은 공정 중에 레지스트에서 플라즈마 에칭 가스 중 이온 및 라디칼이 상기 레지스트막과 복잡한 화학 반응을 일으켜서 레지스트를 급속히 경화시키므로 레지스트의 제거가 곤란하게 된다. 특히 알루미늄, 알루미늄 합금 및 티타늄 나이트라이드와 같은 금속 도전층의 건식 에칭의 경우에 발생하는 변질 경화된 레지스트 폴리머는 웨이퍼의 후면에 부착되어 이후 스트립 공정에서 각종 리무버를 사용하여도 제거하기가 어렵다.The dry etching process replaces a wet etching process using a liquid composition of mixed acid and performs the etching process using a gas phase-solid reaction between a plasma etching gas and a material film such as a conductive layer. Dry etching has become a mainstream of the etching process in recent years because it is easy to control and obtain a sharp pattern. However, dry etching makes it difficult to remove resist because ions and radicals in the plasma etching gas in the resist during the process cause a complex chemical reaction with the resist film to rapidly cure the resist. Particularly in the case of dry etching of metal conductive layers such as aluminum, aluminum alloys and titanium nitride, the modified cured resist polymer is attached to the back side of the wafer and is difficult to remove even with various removers in subsequent strip processes.
따라서, 고집적회로(LSI), 초고집적회로(VLSI) 등의 반도체 디바이스를 제조하는 공정에서는 이러한 불순물을 제거하기 위해 위한 산 세정용액으로 세정하는 침지 공정이 사용된다. 여기에서 리소그래피 공정을 통해 형성한 미세 회로 패턴을 보호하기 위한 보호막 조성물이 필요하며 일반적으로 사용되는 감광성 보호막은 주성분이 수지가 노볼락 계열이기 때문에 산에 의해 쉽게 분해 또는 변성된다.Therefore, in the process of manufacturing a semiconductor device such as a high integrated circuit (LSI), an ultra high integrated circuit (VLSI), an immersion process of cleaning with an acid cleaning solution for removing such impurities is used. Here, a protective film composition for protecting the microcircuit pattern formed through the lithography process is required, and the photosensitive protective film which is generally used is easily decomposed or modified by acid because the main component is a novolak-based resin.
또한, 화학 증폭형 레지스트 (chemical amplification resist)는 산에 의해 쉽게 분해되는 t-BOC 또는 아세탈 등의 작용기(functional group)를 다량 함유하고있어 내산성이 매우 취약하여 감광성 보호막으로는 사용이 불가능하다.In addition, chemical amplification resists contain a large amount of functional groups such as t-BOC or acetal that are easily decomposed by acid, and thus are very weak in acid resistance and thus cannot be used as a photosensitive protective film.
따라서, 내산성을 가짐과 동시에 현상공정 진행 후에도 잔사 불량이 발생되지 않으며 감광 기능이 작용 가능한 보호막용 조성물이 요구되고 있는 실정이다.Therefore, there is a need for a composition for a protective film which has acid resistance and does not cause residue defects even after the development process is progressed.
본 발명은 상기한 문제점을 해결하기 위하여 제안된 것으로서, 본 발명자들은 감광성 보호막으로서 노볼락 수지와 아크릴 수지를 혼합한 수지 시스템을 사용하였고, 이중에서 아크릴 수지의 중량평균 분자량을 특정한 범위대로 조정함으로써 현상공정 진행 후에도 잔사 불량이 발생되지 않으며, 노광후 베이크 (post exposure bake) 온도를 200℃로 하여 아크릴 수지의 경화도를 높이고 내산성이 강화되도록 하는 한편 감광 성분을 도입함으로써 본 발명을 완성하기에 이르렀다.The present invention has been proposed to solve the above problems, and the present inventors used a resin system in which a novolak resin and an acrylic resin were mixed as a photosensitive protective film. Residual defects do not occur even after the progress of the process, and the post exposure bake temperature is set at 200 ° C. to increase the degree of curing of the acrylic resin and to enhance acid resistance, while introducing a photosensitive component, thereby completing the present invention.
따라서, 본 발명은 반도체 디바이스 제조공정중 산 세정용액을 사용한 세정 공정에서 반도체 기판의 미세 회로 패턴을 보호하기 위한 감광성 보호막 조성물을 제공함을 그 목적으로 한다.Accordingly, an object of the present invention is to provide a photosensitive protective film composition for protecting a fine circuit pattern of a semiconductor substrate in a cleaning step using an acid cleaning solution in a semiconductor device manufacturing step.
도 1은 실시예 1의 감광성 보호막 조성물의 내산성 보호성능을 시험한 결과를 광학 현미경으로 촬영한 사진이다.1 is a photograph taken with an optical microscope of the results of testing the acid resistance protective performance of the photosensitive protective film composition of Example 1.
도 2는 비교예 1의 감광성 보호막 조성물의 내산성 보호성능을 시험한 결과를 광학 현미경으로 촬영한 사진이다.2 is a photograph taken with an optical microscope of the results of testing the acid resistance protective performance of the photosensitive protective film composition of Comparative Example 1.
본 발명은 반도체 디바이스 제조공정 중 미세 회로가 형성된 웨이퍼를 산 세정용액으로 웨이퍼 후면을 세정하는 공정에서 산으로부터 미세 회로 패턴을 보호하기 위한 감광성 보호막 조성물에 관한 것으로서, 보다 상세하게는 고분자 수지, 감광성 화합물 및 유기 용매를 포함하는 감광성 보호막 수지 조성물에 있어서, 상기 고분자 수지가 노볼락 수지와 아크릴 수지로 구성되고, 감광성 화합물이 디아지드계 화합물이며, 유기 용매가 에틸 락테이트와 1-메톡시-2-프로판올의 혼합물인 것을 특징으로 한다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive protective film composition for protecting a microcircuit pattern from an acid in a process of cleaning a wafer backside with an acid cleaning solution in a semiconductor device manufacturing process, and more particularly, a polymer resin and a photosensitive compound. And a photosensitive protective film resin composition comprising an organic solvent, wherein the polymer resin is composed of a novolak resin and an acrylic resin, the photosensitive compound is a diazide compound, and the organic solvent is ethyl lactate and 1-methoxy-2-. It is characterized by a mixture of propanols.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 감광성 보호막 조성물은 고분자 수지 15 내지 30 중량%, 감광성 화합물 1.5 내지 5 중량% 및 유기용매 65 내지 83.5 중량%를 포함하는 것이 바람직하다.It is preferable that the photosensitive protective film composition of this invention contains 15-30 weight% of polymeric resins, 1.5-5 weight% of photosensitive compounds, and 65-83.5 weight% of organic solvents.
상기 고분자 수지의 함량이 15 중량% 미만이면 점도가 너무 낮아 일정 두께 이상의 막을 도포 할 수 없기 때문에 산의 침투가 용이해지고, 30 중량%를 초과하면 점도가 너무 높아서 산용액 침지 공정 후에 보호막의 제거가 어렵다는 문제점이 있다.If the content of the polymer resin is less than 15% by weight, the viscosity is so low that it is not possible to apply a film of a predetermined thickness or more, so that the acid is easy to penetrate. There is a problem that is difficult.
상기 감광성 화합물의 함량이 1.5 중량% 미만이면 감광 기능이 제대로 이루어지지 않아 문제가 되고, 5 중량%를 초과하면 산에 대한 보호 능력이 저하되는 문제점이 있다.When the content of the photosensitive compound is less than 1.5% by weight, the photosensitive function is not properly performed, and when the content of the photosensitive compound exceeds 5% by weight, there is a problem in that the protection against acid is lowered.
본 발명의 감광성 보호막 조성물에 사용되는 고분자 수지는 노볼락 수지와 아크릴 수지로 이루어진다. 고분자 수지는 노볼락 수지와 아크릴 수지를 1 : 1 내지 1.5 : 1 의 중량비로 구성되는 것이 바람직하다. 상기 노볼락 수지와 아크릴 수지의 중량비가 1 : 1 내지 1.5 : 1의 비율을 벗어나게 되면 감광성 보호막의 내산성이 저하되는 문제점이 있다.The polymer resin used for the photosensitive protective film composition of this invention consists of a novolak resin and an acrylic resin. The polymer resin is preferably composed of a novolak resin and an acrylic resin in a weight ratio of 1: 1 to 1.5: 1. When the weight ratio of the novolac resin and the acrylic resin is out of the ratio of 1: 1 to 1.5: 1, there is a problem in that acid resistance of the photosensitive protective film is lowered.
상기 노볼락 수지는 메타 및/또는 파라 크레졸 등의 방향족 알콜과 포름 알데히드를 반응시켜 합성한 고분자 중합체로서, 본 발명에 사용되는 노볼락 수지는 메타 크레졸과 파라 크레졸을 60 중량부 : 40 중량부 내지 40 중량부 : 60 중량부로 포름 알데히드와 반응시켜 합성한 고분자 중합체를 포함하는 것이 바람직하다.The novolak resin is a polymer polymer synthesized by reacting an aromatic alcohol such as meta and / or paracresol with formaldehyde. The novolak resin used in the present invention is 60 parts by weight of 40 parts by weight of metacresol and paracresol. 40 parts by weight: It is preferable to include a high molecular polymer synthesized by reacting with formaldehyde at 60 parts by weight.
상기 아크릴 수지는 2-히드록시에틸 아크릴레이트, 메틸메타크릴레이트, 메타크릴산과 아조비스이소부틸니트릴 (azobisisobutylnitrile : AIBN)을 반응시켜 합성한 고분자 중합체로서, 본 발명에 사용되는 아크릴 수지는 2-히드록시에틸 아크릴레이트 10 내지 30 중량%, 메틸메타크릴레이트 50 내지 80 중량% 및 메타크릴산 10 내지 30 중량%를 반응시켜 제조되며 중합체의 중량 평균 분자량이 20,000 ∼ 50,000 임을 특징으로 한다.The acrylic resin is a high molecular polymer synthesized by reacting 2-hydroxyethyl acrylate, methyl methacrylate, methacrylic acid and azobisisobutylnitrile (AIBN), and the acrylic resin used in the present invention is 2-hydroxy. It is prepared by reacting 10 to 30% by weight of oxyethyl acrylate, 50 to 80% by weight of methyl methacrylate and 10 to 30% by weight of methacrylic acid, characterized in that the polymer has a weight average molecular weight of 20,000 to 50,000.
중합체의 중량 평균 분자량이 20,000 이하인 경우는 내산성이 떨어져 사용이 불가능하고 50,000 이상인 경우는 현상공정 후 잔사가 남는 불량을 일으킨다.If the weight average molecular weight of the polymer is 20,000 or less, the acid resistance is not available, and if it is 50,000 or more, the residue remains after the developing process.
또한, 보호막 성능 개선을 위하여, 상기 중합체를 합성하는데 있어서 반응 온도 또는 시간을 변화시켜 용도에 적합한 분자량을 가지는 수지를 선택하여 사용할 수도 있다.In addition, in order to improve the protective film performance, a resin having a molecular weight suitable for the application may be selected and used by changing the reaction temperature or time in synthesizing the polymer.
본 발명의 감광성 보호막 조성물에 사용되는 감광성 화합물은 디아지드계 화합물로서, 상기 디아지드계 화합물은 하기 화학식 1로 표시되는 것이 바람직하다.The photosensitive compound used in the photosensitive protective film composition of the present invention is a diazide compound, and the diazide compound is preferably represented by the following formula (1).
[화학식 1][Formula 1]
(상기 화학식에서, R1, R2, R3및 R4는 알킬기 또는 벤질기이고, R5, R6, R7및 R8은 2-디아조-1-나프톨-5-술포닐 또는 수소이다.)(Wherein R 1 , R 2 , R 3 and R 4 are alkyl or benzyl groups, and R 5 , R 6 , R 7 and R 8 are 2-diazo-1-naphthol-5-sulfonyl or hydrogen to be.)
상기 디아지드계 화합물은 하기 화학식 2의 화합물과 2-디아조-1-나프톨-5-술폰산 등의 디아지드계 화합물을 반응시켜 제조할 수 있다:The diazide compound may be prepared by reacting a compound of Formula 2 with a diazide compound such as 2-diazo-1-naphthol-5-sulfonic acid.
[화학식 2][Formula 2]
본 발명의 감광성 보호막 조성물에 사용되는 유기 용매는 에틸 락테이트와 1-메톡시-2-프로판올의 혼합물인 것을 특징으로 한다. 본 발명의 연구자들이 검토한 결과 에틸 락테이트의 경우 아크릴 수지에 대한 용해성이 뛰어나며 1-메톡시-2-프로판올의 경우 상기 디아지드계 화합물에 대한 용해성이 탁월함을 발견하였고 이들의 혼합물을 용매로 사용하는 경우 최적의 성능을 발휘함을 알 수 있었다. 통상적으로 레지스트에 범용적으로 사용되는 유기 용매인 프로필렌글리콜 모노메틸에테르아세테이트는 아크릴 수지에 대한 용해성이 전혀 없고 에틸에톡시 프로피오네이트와 메틸메톡시 프로피오네이트 등의 용매를 사용할 경우, 같은 조건에서의 필름 막의 두께가 얇아지기 때문에, 산에 대한 보호 능력이 저하되는 문제점이 있다. 상기 용매는 1-메톡시-2-프로판올과 에틸 락테이트를 70:30 내지 90:10의 중량비로 포함하는 것이 바람직하다.The organic solvent used in the photosensitive protective film composition of the present invention is characterized by being a mixture of ethyl lactate and 1-methoxy-2-propanol. As a result of the investigation by the researchers of the present invention, ethyl lactate has excellent solubility in acrylic resin and 1-methoxy-2-propanol has excellent solubility in the diazide compound, and a mixture thereof is used as a solvent. It was found that the best performance. Generally, propylene glycol monomethyl ether acetate, an organic solvent commonly used in resists, has no solubility in acrylic resins, and solvents such as ethyl ethoxy propionate and methyl methoxy propionate are used under the same conditions. Since the film thickness of a film becomes thin, there exists a problem that the ability to protect against an acid falls. The solvent preferably contains 1-methoxy-2-propanol and ethyl lactate in a weight ratio of 70:30 to 90:10.
상기 본 발명의 감광성 보호막 조성물은 다음과 같이 반도체 공정에 사용된다.The photosensitive protective film composition of the present invention is used in a semiconductor process as follows.
상기 감광성 보호막 조성물을 미세 회로 패턴이 형성된 기판에 침지, 분무,회전 및 스핀 코팅을 포함하는 통상적인 방법으로 도포한다. 예를 들면 스핀 코팅의 경우, 감광성 보호막 조성물의 성분 중 고체 함량을 스피닝 장치의 종류와 방법에 따라 적절히 변화 시킴으로써 목적하는 두께의 피복물을 형성할 수 있다. 상기 기판으로는 실리콘, 실리콘 나이트라이드, 아모폴스 실리콘 등 각종 기판을 사용할 수 있다.The photosensitive protective film composition is applied to a substrate on which a fine circuit pattern is formed by a conventional method including dipping, spraying, rotating, and spin coating. For example, in the case of spin coating, a coating having a desired thickness can be formed by appropriately changing the solids content in the components of the photosensitive protective film composition according to the type and method of the spinning device. As the substrate, various substrates such as silicon, silicon nitride, amorphous silicon, and the like can be used.
상기 방법에 의하여 기판에 코팅된 내산성 감광성 보호막 조성물을 50 내지 120 ℃의 온도로 가열한다. 이를 소프트 베이크(soft bake) 공정이라 하며 이러한 처리는 포토레지스트 조성물 중 고체 성분을 열분해 시키지 않으면서 용매를 증발시키기 위한 것이다. 소프트 베이크 공정을 통하여 용매의 농도를 최소화하는 것이 바람직하다. 따라서 상기 열처리는 대부분의 용매가 증발되어 감광성 보호막 조성물의 얇은 피복막이 기판에 남을 때까지 수행하는 것이 바람직하다.The acid resistant photosensitive protective film composition coated on the substrate by the above method is heated to a temperature of 50 to 120 ℃. This is called a soft bake process and this treatment is for evaporating the solvent without pyrolyzing the solid components in the photoresist composition. It is desirable to minimize the concentration of solvent through the soft bake process. Therefore, the heat treatment is preferably performed until most of the solvent is evaporated so that a thin coating film of the photosensitive protective film composition remains on the substrate.
다음으로, 감광성 보호막이 형성된 기판을 적당한 마스크 또는 형판 등을 사용하여 빛, 특히 자외선에 노광 시킴으로써 목적하는 부분만 피복만이 남도록 패턴을 형성한다. 다음으로 기판에 도포된 보호막 조성물을 100 내지 200 ℃의 온도로 가열한다. 이를 노광후 베이크 (post exposure bake) 공정이라 한다. 이러한 열처리를 수행함으로써 감광성 보호막의 접착성 및 내화학성을 증진시킬 수 있다.Next, the substrate on which the photosensitive protective film is formed is exposed to light, in particular ultraviolet rays, using a suitable mask or template to form a pattern such that only a desired portion remains. Next, the protective film composition apply | coated to the board | substrate is heated to the temperature of 100-200 degreeC. This is called a post exposure bake process. By performing such heat treatment, the adhesion and chemical resistance of the photosensitive protective film can be enhanced.
노광된 기판을 알칼리성 현상액에 충분히 침지시킨 후, 빛에 노출된 부위의 감광성 보호막이 전부 또는 거의 대부분 용해될 때까지 방치한다. 적합한 현상액은 알칼리 수산화물, 수산화암모늄 또는 테트라메틸암모늄 하이드록사이드를 함유하는 수용액이다.The exposed substrate is sufficiently immersed in an alkaline developer, and left to stand until all or almost all of the photosensitive protective film at the site exposed to light is dissolved. Suitable developer is an aqueous solution containing alkali hydroxide, ammonium hydroxide or tetramethylammonium hydroxide.
노광된 부위가 용해되어 제거된 기판을 현상액으로부터 꺼낸 후, 상기 반도체 기판을 불산, 인산, 과산화수소 및 초순수가 포함된 혼합 산 세정용액에 침지 시켜서 반도체 기판 위의 불순물을 세척하여 제거한다. 그 다음, 상기 세척된 반도체 기판을 황산, 과산화수소수, 및 초순수의 혼합 용액에 침지 시켜 잔류되어 있는 감광성 보호막을 제거시킨다.After removing the substrate from which the exposed part is dissolved and removed, the semiconductor substrate is immersed in a mixed acid cleaning solution containing hydrofluoric acid, phosphoric acid, hydrogen peroxide and ultrapure water to remove impurities on the semiconductor substrate by washing. The washed semiconductor substrate is then immersed in a mixed solution of sulfuric acid, hydrogen peroxide water and ultrapure water to remove the remaining photosensitive protective film.
이하, 본 발명을 하기 실시예 및 비교예를 참조로 하여 보다 상세히 설명한다. 그러나, 이들 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명이 이들 예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following Examples and Comparative Examples. However, these examples are only for illustrating the present invention, and the present invention is not limited to these examples.
[합성예]Synthesis Example
1000 ml의 4구 둥근 바닥 플라스크에 교반기, 콘덴서, 온도계 그리고 질소가스주입구를 설치하였다. 질소가스 분위기 하에서 2-히드록시에틸 아크릴레이트 40 g, 메틸메타크릴레이트 80 g, 메타크릴산 30 g을 에틸 락테이트 200 g과 함께 넣고 교반하며 80℃로 중탕 가열하였다. 10 g의 에틸 락테이트에 촉매 아조비스이소부틸니트릴 1.0 g을 녹인 후 이 용액을 적하하고 4 시간 동안 70 ℃에서 중합반응시켰다. 이와 같은 방법으로 얻어진 아크릴 수지 용액을 그대로 감광성 보호막 조성물 제조에 이용하였다.A 1000 ml four-necked round bottom flask was equipped with a stirrer, condenser, thermometer and nitrogen gas inlet. 40 g of 2-hydroxyethyl acrylate, 80 g of methyl methacrylate, and 30 g of methacrylic acid were added together with 200 g of ethyl lactate under a nitrogen gas atmosphere, followed by stirring and heating at 80 ° C. 1.0 g of the catalyst azobisisobutylnitrile was dissolved in 10 g of ethyl lactate, and this solution was added dropwise and polymerized at 70 ° C for 4 hours. The acrylic resin solution obtained by such a method was used for the manufacture of the photosensitive protective film composition as it is.
[표 1]TABLE 1
2-HEA : 2-히드록시에틸 아크릴레이트2-HEA: 2-hydroxyethyl acrylate
MMA : 메틸메타크릴레이트MMA: Methyl methacrylate
MA : 메타크릴산MA: Methacrylic acid
[실시예 1 내지 5 및 비교예 1 내지 3][Examples 1 to 5 and Comparative Examples 1 to 3]
회로가 형성되어 있는 실리콘 (Si) 웨이퍼에 하기 표 2에 기재된 조성의 감광성 보호막 조성물을 적하 하고, 일정한 회전 속도로 회전시킨 후, 상기 웨이퍼를 90 ℃에서 60 초간 가열 건조하여 2 내지 3 ㎛ 두께의 필름막을 형성하였다. 상기 필름막 상에 소정 형상의 마스크를 장착한 다음, 자외선을 조사하고, 테트라메틸암모늄 하이드록사이드 2.38 중량% 수용액에 60 초 동안 침적시켜 자외선에 노광된 부분을 제거한 후 불산, 인산, 과산화수소 및 초순수가 포함된 혼합 산 용액에 온도를 42 내지 44 ℃로 하여 시간별로 침지 시켜, 반도체 기판의 후면 및 노광된 부분의 불순물을 제거하고, 이어서 초순수를 사용하여 상기 반도체 기판 위의 잔류 산 성분을 세척하여 제거하고, 질소로 건조한 후에 광학 현미경으로 산으로부터의 보호능력을 확인하고 이를 하기 표 3 및 도 1 내지 2에 나타내었다.The photosensitive protective film composition of the composition shown in following Table 2 was dripped at the silicon (Si) wafer in which the circuit was formed, and it rotates at a fixed rotational speed, and then heat-drys the said wafer at 90 degreeC for 60 second, and has a thickness of 2-3 micrometers. A film film was formed. After mounting a mask having a predetermined shape on the film film, it was irradiated with ultraviolet rays, and then immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds to remove the portion exposed to ultraviolet rays, followed by hydrofluoric acid, phosphoric acid, hydrogen peroxide and ultrapure water. Impregnated with the mixed acid solution contained at a temperature of 42 to 44 ℃ by time to remove impurities in the back and exposed portions of the semiconductor substrate, followed by washing the residual acid component on the semiconductor substrate with ultrapure water And, after drying with nitrogen to confirm the protection from the acid under an optical microscope and this is shown in Table 3 and Figures 1-2.
[표 2]TABLE 2
PGMEA : 프로필렌글리콜 모노메틸에테르아세테이트PGMEA: Propylene Glycol Monomethyl Ether Acetate
MMP : 메틸테톡시프로피오네이트MMP: Methyltethoxypropionate
EL : 에틸락테이트EL: ethyl lactate
[표 3]TABLE 3
상기한 바와 같이, 본 발명의 감광성 보호막 조성물은 산에 대한 보호능력이 뛰어날 뿐 아니라 현상공정 진행 후에도 잔사 불량이 발생되지 않으며 감광성 물질을 포함하고 있어 추가적인 보호막 코팅 및 제거 공정이 필요 없으므로, 생산성을 극대화할 수 있으며, 제품 불량률을 최소화할 수 있는 장점이 있다.As described above, the photosensitive protective film composition of the present invention not only has excellent protection against acid, but also does not cause residue defects even after the development process and includes a photosensitive material, thus requiring no additional protective film coating and removing process, thereby maximizing productivity. It can be, and there is an advantage that can minimize the product failure rate.
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| US5372912A (en) * | 1992-12-31 | 1994-12-13 | International Business Machines Corporation | Radiation-sensitive resist composition and process for its use |
| JP3583217B2 (en) * | 1995-04-11 | 2004-11-04 | コダックポリクロームグラフィックス株式会社 | Photosensitive composition and photosensitive lithographic printing plate |
| JP3556756B2 (en) * | 1995-04-11 | 2004-08-25 | コダックポリクロームグラフィックス株式会社 | Photosensitive composition and photosensitive lithographic printing plate |
| JPH08283455A (en) * | 1995-04-17 | 1996-10-29 | Toagosei Co Ltd | Production of positive type resist composition |
| JP3471990B2 (en) * | 1995-09-27 | 2003-12-02 | 富士写真フイルム株式会社 | Positive photosensitive lithographic printing plate and method for producing the same |
-
2000
- 2000-11-08 KR KR10-2000-0066127A patent/KR100481012B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021094423A1 (en) * | 2019-11-14 | 2021-05-20 | Merck Patent Gmbh | Dnq-type photoresist composition including alkali-soluble acrylic resins |
| US11822242B2 (en) | 2019-11-14 | 2023-11-21 | Merck Patent Gmbh | DNQ-type photoresist composition including alkali-soluble acrylic resins |
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| Publication number | Publication date |
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| KR100481012B1 (en) | 2005-04-06 |
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