CN105723284A - Resist remover liquid - Google Patents
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- CN105723284A CN105723284A CN201480059453.XA CN201480059453A CN105723284A CN 105723284 A CN105723284 A CN 105723284A CN 201480059453 A CN201480059453 A CN 201480059453A CN 105723284 A CN105723284 A CN 105723284A
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- 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
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
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Abstract
经干蚀刻而变质的抗蚀膜牢固地附着在涂布面上，并且利用将铜膜上的抗蚀膜剥离的抗蚀剂剥离液不能完全剥离。另一方面，剥离力强的铝膜用的剥离液腐蚀铜膜。期望一种抗蚀剂剥离液，其能够剥离因等离子体而变质的抗蚀膜，并且无论基底是铜膜还是铝膜，实质上都不腐蚀。一种抗蚀剂剥离液，其特征在于，含有链烷醇叔胺、极性溶剂、水、环式胺以及糖醇，所述抗蚀剂剥离液能够剥离因干蚀刻而变质的抗蚀膜，并且无论基底是铜膜还是铝膜，实质上都不腐蚀。The resist film degraded by dry etching firmly adheres to the coated surface, and cannot be completely peeled off by a resist stripping liquid that peels off the resist film on the copper film. On the other hand, the stripping solution for the aluminum film with strong peeling force corrodes the copper film. A resist stripping solution that can strip a resist film degraded by plasma and substantially does not corrode regardless of whether the substrate is a copper film or an aluminum film is desired. A resist stripping solution, characterized in that it contains alkanol tertiary amines, polar solvents, water, cyclic amines and sugar alcohols, and the resist stripping solution can strip the resist film deteriorated due to dry etching , and no matter whether the substrate is a copper film or an aluminum film, it does not corrode substantially.
Description
技术领域technical field
本发明为用于剥离在液晶、有机EL等显示装置、半导体的制造时使用的抗蚀剂的剥离液，更详细而言，涉及如下抗蚀剂剥离液，可以说其能够去除在干蚀刻中暴露于等离子体中的抗蚀剂，进而对铝膜和铜膜实质上也不腐蚀。The present invention relates to a stripping solution for stripping a resist used in the manufacture of display devices such as liquid crystals and organic ELs, and semiconductors. More specifically, it relates to a resist stripping solution that can be removed by dry etching. The resist exposed to plasma does not substantially corrode the aluminum film and the copper film.
背景技术Background technique
在液晶、有机EL(电致发光(Electro-Luminescence))等平板显示器(FPD)的TFT(薄膜晶体管(ThinFilmTransistor))制造工艺中，为了形成导电布线，使用利用光刻法的蚀刻。In the TFT (Thin Film Transistor) manufacturing process of flat panel displays (FPDs) such as liquid crystals and organic EL (Electro-Luminescence), etching by photolithography is used to form conductive wiring.
该蚀刻中，例如在成膜后的金属膜上形成抗蚀膜。对于抗蚀膜，通过图案掩模而被曝光并显影，从而想要利用蚀刻而残留的图案(或其负像图案)残留在膜上。然后，通过利用了等离子体等的干蚀刻去除露出的金属膜。然后用抗蚀剂剥离液将保护了金属膜免受干蚀刻的、经图案化的抗蚀膜剥离。In this etching, for example, a resist film is formed on the formed metal film. The resist film is exposed and developed through a pattern mask, so that the pattern (or its negative image pattern) intended to be left by etching remains on the film. Then, the exposed metal film is removed by dry etching using plasma or the like. The patterned resist film, which protected the metal film from dry etching, is then stripped with a resist stripping solution.
以往的导电布线主要由铝形成。但是，因FPD的大型化而需要使大量电流流过，已经研究了将电阻率更小的铜作为导电布线使用。Conventional conductive wiring is mainly formed of aluminum. However, due to the increase in the size of the FPD, it is necessary to flow a large amount of current, and it has been studied to use copper having a lower resistivity as the conductive wiring.
但是，铜往往被抗蚀剂剥离液腐蚀，对于使铜膜上形成的抗蚀膜剥离的抗蚀剂剥离液，需要使抗蚀膜剥离，并且抑制铜的腐蚀。因此，提出了一种抗蚀剂剥离液，其含有苯并三唑作为铜的缓蚀剂。另外，除此之外，哌嗪的化合物作为能够剥离抗蚀剂而且对铜的腐蚀也少的物质被提出(专利文献1、专利文献2)。However, copper is often corroded by a resist stripping solution, and the resist stripping solution for stripping a resist film formed on a copper film needs to strip the resist film and suppress copper corrosion. Therefore, a resist stripping solution containing benzotriazole as a copper corrosion inhibitor has been proposed. In addition, piperazine compounds have been proposed as substances capable of stripping resists and less corroding copper (Patent Document 1, Patent Document 2).
另一方面，在FPD中，也有用铝进行布线的部分，剥离铝膜上的抗蚀膜和剥离铜膜上的抗蚀膜的抗蚀剂剥离液分别单独进行制备。On the other hand, in the FPD, also in the portion where aluminum is used for wiring, resist stripping liquids for peeling off the resist film on the aluminum film and the resist film on the copper film were prepared separately.
共有铝膜和铜膜上的抗蚀膜的剥离液这种问题的提起可以追溯到专利文献1的时代。专利文献3中公开了如下技术：对铝和铜进行选择蚀刻时，使质子给予性的有机溶剂或质子接受性的有机溶剂在室温以上与剥离对象抗蚀膜缔合，与氧化性物质在水分1000ppm以上的环境中放置。The problem of sharing the stripping solution of the resist film on the aluminum film and the copper film can be traced back to the era of Patent Document 1. Patent Document 3 discloses a technique in which a proton-donating organic solvent or a proton-accepting organic solvent is associated with a resist film to be stripped at room temperature or higher when selectively etching aluminum and copper, and an oxidizing substance is dissolved in moisture. Placed in an environment above 1000ppm.
此外，专利文献4中公开了剥离铜膜上的抗蚀膜的抗蚀剂剥离液。专利文献4中公开了含有胺、溶剂、强碱以及水的抗蚀剂剥离液。在专利文献4中，通过在氧浓度为规定值以下的环境下使用这些组成的抗蚀剂剥离液，防止了铜的腐蚀。In addition, Patent Document 4 discloses a resist stripping solution for stripping a resist film on a copper film. Patent Document 4 discloses a resist stripping solution containing an amine, a solvent, a strong base, and water. In Patent Document 4, corrosion of copper is prevented by using a resist stripping solution having these compositions in an environment where the oxygen concentration is not more than a predetermined value.
此外，专利文献5是为了解决经干蚀刻工艺的抗蚀膜变质而不易被显影时的溶液剥离的问题而想到的技术。其中公开了由胺、醚、糖醇、季铵以及水构成的抗蚀剂剥离液。需要说明的是，在专利文献4中，对于抗蚀膜的形成，假定在铝膜上，但没有假定在铜上。In addition, Patent Document 5 is a technique conceived to solve the problem that the resist film undergoes a dry etching process deteriorates and is not easily peeled off by a solution during development. Therein, a resist stripping solution composed of amine, ether, sugar alcohol, quaternary ammonium, and water is disclosed. In addition, in Patent Document 4, formation of a resist film is assumed to be on an aluminum film, but not on copper.
现有技术文献prior art literature
专利文献patent documents
专利文献1：日本特开昭60-131535号公报Patent Document 1: Japanese Patent Laid-Open No. 60-131535
专利文献2：日本特开2006-079093号公报Patent Document 2: Japanese Patent Laid-Open No. 2006-079093
专利文献3：日本特开平05-047654号公报Patent Document 3: Japanese Patent Application Laid-Open No. 05-047654
专利文献4：日本特开2003-140364号公报Patent Document 4: Japanese Patent Laid-Open No. 2003-140364
专利文献5：日本特开平08-262746号公报Patent Document 5: Japanese Patent Application Laid-Open No. 08-262746
发明内容Contents of the invention
发明要解决的问题The problem to be solved by the invention
如专利文献5中所提及的，经干蚀刻工艺的抗蚀膜变质、不易剥离。因此，需要在伯胺或仲胺那样的强碱下使用剥离力强的抗蚀剂剥离液。As mentioned in Patent Document 5, the resist film after the dry etching process deteriorates and is not easily peeled off. Therefore, it is necessary to use a resist stripping solution with strong stripping force under strong alkali such as primary or secondary amine.
在使用这样的剥离力强的抗蚀剂剥离液的情况下，基底为铝膜时，不怎么被腐蚀。但是，基底为铜膜时，被腐蚀。需要说明的是，此处，基底包括在剥离抗蚀膜时处于直接暴露于抗蚀剂剥离液中的状态的膜。In the case of using such a resist stripping liquid having a strong peeling force, the substrate is not corroded so much when the aluminum film is used. However, when the base is a copper film, it is corroded. Here, the base includes a film that is directly exposed to a resist stripping solution when the resist film is stripped.
即，伯胺或仲胺一方面能够使正型抗蚀剂中利用的酚醛清漆树脂和作为碱不溶化剂的重氮萘醌化合物溶解于极性溶剂、水中，另一方面也会使铜溶解。That is, primary or secondary amines can dissolve the novolac resin used in positive resists and the diazonaphthoquinone compound as an alkali insolubilizer in polar solvents and water, and can also dissolve copper.
因此，目前，在铜膜为基底的情况下，剥离经干蚀刻工艺的抗蚀膜时，在用灰化等技术去除规定膜厚的抗蚀膜后，使用抗蚀剂剥离液。Therefore, conventionally, when removing a resist film subjected to a dry etching process when a copper film is used as a base, a resist stripping solution is used after removing a predetermined thickness of the resist film by ashing or the like.
在FPD的制造中，混合存在有使用铜膜的产品和使用铝膜的产品。因此，只要能够用1种抗蚀剂剥离液使铝和铜上形成的抗蚀膜剥离，就可以将剥离工序生产线设为1个。此外，由于抗蚀剂剥离液的管理也能够一元化，因此不仅在制造工序上非常优选，而且还有助于减少成本。In the manufacture of FPDs, products using a copper film and products using an aluminum film are mixed. Therefore, as long as the resist films formed on aluminum and copper can be peeled off with one type of resist stripping solution, one stripping process line can be used. In addition, since the management of the resist stripping liquid can also be unified, it is not only very preferable in the production process, but also contributes to cost reduction.
专利文献1、2提及了提供如下的抗蚀剂剥离液，其将蚀刻工序中变质而难以剥离的抗蚀剂剥离，而且不腐蚀金属布线。然而，实际上，改变基底的金属的种类，确认不到剥离性、腐蚀性。Patent Documents 1 and 2 refer to providing a resist stripping solution that strips a resist that has deteriorated in an etching process and is difficult to strip without corroding metal wiring. However, in reality, peelability and corrosion were not confirmed by changing the type of metal of the base.
专利文献3为关于铝和铜同时存在的状态下的抗蚀剂剥离的发明。但是，仅仅公开了具有烷基苯磺酸作为质子给予性的有机溶剂、并且含有单乙醇胺作为质子接受性的有机溶剂的剥离液，并没有公开具体的组成。Patent Document 3 is an invention related to resist stripping in a state where aluminum and copper coexist. However, only a stripping solution containing alkylbenzenesulfonic acid as a proton-donating organic solvent and monoethanolamine as a proton-accepting organic solvent is disclosed, and no specific composition is disclosed.
虽然专利文献4提及了关于铜膜上的抗蚀膜的剥离，但没有提及关于能够与铝膜上的抗蚀膜的剥离液共用的方面。Although Patent Document 4 mentions the stripping of the resist film on the copper film, it does not mention the point that it can be shared with the stripping liquid of the resist film on the aluminum film.
即，没有提出能够剥离因等离子体而变质的抗蚀膜、且无论基底为铜膜还是铝膜实质上都不腐蚀的抗蚀剂剥离液。That is, no resist stripping solution has been proposed that can strip a resist film degraded by plasma without substantially corroding a copper film or an aluminum film as a base.
用于解决问题的方案solutions to problems
本发明是鉴于上述问题而想到的，提供一种抗蚀剂剥离液，其能够剥离在干蚀刻时暴露于等离子体中而变质的抗蚀膜，进而，无论基底为铝膜还是铜膜，都将腐蚀减少到实质上不成为问题的程度。The present invention is conceived in view of the above-mentioned problems, and provides a resist stripping solution capable of stripping a resist film degraded by exposure to plasma during dry etching, and furthermore, regardless of whether the substrate is an aluminum film or a copper film, Corrosion is reduced to a point where it is not substantially a problem.
更具体的而言，本发明的抗蚀剂剥离液的特征在于，More specifically, the resist stripping solution of the present invention is characterized in that
含有链烷醇叔胺、极性溶剂、水、环式胺以及糖醇。此外，也可以使用一部分仲胺来替换环式胺。Contains tertiary alkanol amines, polar solvents, water, cyclic amines and sugar alcohols. In addition, a part of secondary amines may be used instead of cyclic amines.
发明的效果The effect of the invention
本发明的抗蚀剂剥离液能够剥离在干蚀刻时暴露于等离子体中而变质的抗蚀膜。另一方面，提供一种无论基底为铜膜还是铝膜、实质上都能够接受的腐蚀程度的抗蚀剂剥离液。The resist stripping solution of the present invention can strip a resist film degraded by exposure to plasma during dry etching. On the other hand, there is provided a resist stripping solution having a substantially acceptable level of corrosion regardless of whether the substrate is a copper film or an aluminum film.
因此，无论是铝膜上的抗蚀膜还是铜膜上的抗蚀膜，都能够用1种抗蚀剂剥离液进行剥离。即，不必准备多种抗蚀膜的剥离工序生产线，此外抗蚀剂剥离液也为1种管理即可。此外，也不需要被称为灰化的工序。其结果能够对工厂的生产率及成本的减少有较大贡献。Therefore, both the resist film on the aluminum film and the resist film on the copper film can be stripped with one resist stripping solution. That is, it is not necessary to prepare a stripping process line for a plurality of types of resist films, and it is only necessary to manage one type of resist stripping solution. In addition, a process called ashing is also unnecessary. As a result, it can greatly contribute to the reduction of the productivity and cost of a factory.
具体实施方式detailed description
以下对本发明的抗蚀剂剥离液进行说明。需要说明的是，以下的说明示出本发明的抗蚀剂剥离液的一个实施方式，在不脱离本发明的宗旨的范围内，可以改变以下的实施方式及实施例。The resist stripping solution of the present invention will be described below. In addition, the following description shows one embodiment of the resist stripping liquid of this invention, and the following embodiment and an Example can be changed in the range which does not deviate from the summary of this invention.
设想本发明的抗蚀剂剥离液所剥离的抗蚀膜为正型抗蚀剂。在正型抗蚀剂中，含有酚醛清漆系树脂作为树脂，且使用重氮萘醌(以下记为“DNQ”。)化合物作为光敏剂。在进行蚀刻时，在基板上形成抗蚀膜，隔着图案进行曝光。It is assumed that the resist film stripped by the resist stripping solution of the present invention is a positive resist. In the positive resist, a novolac resin is contained as a resin, and a diazonaphthoquinone (hereinafter referred to as "DNQ") compound is used as a photosensitizer. When performing etching, a resist film is formed on a substrate, and exposure is performed through a pattern.
通过该曝光，DNQ化合物变为茚酮。若茚酮与水缔合，则转变为茚羧酸而溶解于水中。酚醛清漆系树脂原本具有溶于碱溶液的性质，但溶解点被DNQ保护。DNQ因曝光而变质并在水中溶出，从而酚醛清漆树脂也溶出。如此，完成抗蚀膜的图案化。By this exposure, the DNQ compound becomes indanone. When indene is associated with water, it is transformed into indene carboxylic acid and dissolved in water. The novolak-based resin originally has the property of being soluble in an alkali solution, but the melting point is protected by DNQ. DNQ is deteriorated by exposure and is eluted in water, so that novolak resin is also eluted. In this way, patterning of the resist film is completed.
对利用抗蚀膜完成了图案化的基板实施湿蚀刻处理或干蚀刻处理。干蚀刻为在真空中进行的处理，以图案的形式残留的抗蚀膜被暴露于高温和自由基的气氛中。由此，抗蚀膜中的酚醛清漆系树脂彼此进行再结合，变质为不易溶解的组成。Wet etching or dry etching is performed on the substrate patterned with the resist film. Dry etching is a process performed in a vacuum, and the resist film remaining in the form of a pattern is exposed to a high temperature and a radical atmosphere. As a result, the novolak-based resins in the resist film are recombined with each other, and are changed into a composition that is not easily soluble.
由于蚀刻后不需要抗蚀膜，因此用抗蚀剂剥离液进行剥离。即，抗蚀剂剥离液所剥离的抗蚀膜也以经干蚀刻工序的抗蚀膜为对象。需要说明的是，残留于基板上的抗蚀膜不经过曝光的工序，但在蚀刻结束后被暴露于等离子体中或放置在荧光灯下，从而变成抗蚀膜整体被曝光的状态。Since the resist film was unnecessary after etching, it was stripped with a resist stripper. That is, the resist film stripped by the resist stripping solution also applies to the resist film that has undergone the dry etching process. It should be noted that the resist film remaining on the substrate is not subjected to the exposure step, but is exposed to plasma or placed under a fluorescent lamp after the etching, so that the entire resist film is exposed.
抗蚀剂剥离液成为问题的方面为以下的方面。作为例子，以制作FET(场效应晶体管(FieldEffectTransistor))的基本工艺进行说明。在基板上，用铜、铝将格栅等的布线制成图案。其经过通过湿蚀刻去除铜、铝的工序。此时，用抗蚀剂剥离液能够去除残留在铜、铝的图案上的抗蚀剂。此时，铜、铝由于与抗蚀剂剥离液接触而被腐蚀。The resist stripping liquid becomes a problem in the following points. As an example, the basic process of manufacturing FET (Field Effect Transistor (FieldEffectTransistor)) will be described. On the substrate, wiring such as a grid is patterned with copper or aluminum. It passes through the process of removing copper and aluminum by wet etching. At this time, the resist remaining on the copper and aluminum patterns can be removed with a resist stripping solution. At this time, copper and aluminum are corroded by contact with the resist stripping solution.
接着，在铜膜、铝膜的图案上将SiNx层成膜作为绝缘层，在SiNx层上将作为半导体部分的a-Si(n+)/a-Si(非晶硅)层成膜。将a-Si(n+)/a-Si层的抗蚀剂涂布、曝光、显影，并通过干蚀刻来进行a-Si(n+)/a-Si层的图案化。然后，用抗蚀剂剥离液去除抗蚀剂，但进行干蚀刻时的暴露于等离子体中的抗蚀膜如上述所说明地发生变质，不易溶解。Next, a SiNx layer is formed as an insulating layer on the pattern of the copper film and the aluminum film, and an a-Si(n+)/a-Si (amorphous silicon) layer as a semiconductor part is formed on the SiNx layer. A resist for the a-Si(n+)/a-Si layer was applied, exposed, developed, and dry-etched to pattern the a-Si(n+)/a-Si layer. Thereafter, the resist is removed with a resist stripping solution, but the resist film exposed to plasma during dry etching is deteriorated as described above and is difficult to dissolve.
接着，在a-Si(n+)/a-Si层上成膜SD(源级/漏级)布线用的金属膜，在金属膜上将抗蚀剂涂布、曝光、显影，并通过湿蚀刻来进行SD布线的图案化。然后通过干蚀刻去除a-Si(n+)层，形成a-Si层的沟道。在这种情况下也是，进行干蚀刻时的暴露于等离子体中的抗蚀膜发生变质、不易溶解。然后，用抗蚀剂剥离液去除残留在铜膜、铝膜的图案上的抗蚀膜。在这种情况下也是，铜膜、铝膜由于与抗蚀剂剥离液接触而被腐蚀。Next, a metal film for SD (source/drain) wiring is formed on the a-Si(n+)/a-Si layer, a resist is applied on the metal film, exposed, developed, and wet-etched To pattern the SD wiring. The a-Si(n+) layer is then removed by dry etching to form a channel for the a-Si layer. Even in this case, the resist film exposed to the plasma during dry etching is deteriorated and hardly dissolves. Then, the resist film remaining on the pattern of the copper film and the aluminum film is removed with a resist stripping solution. Also in this case, the copper film and the aluminum film are corroded by contact with the resist stripping solution.
进行干蚀刻时的暴露于等离子体中的抗蚀膜如上述所说明地发生变质、不易溶解。因此，若使用能够剥离变质的抗蚀膜程度的强力抗蚀剂剥离液，则湿蚀刻后的金属布线(特别是铜膜)受到腐蚀。另一方面，若为金属布线(铜膜)不被腐蚀的程度的抗蚀剂剥离液，则无法剥离变质的抗蚀膜。The resist film exposed to the plasma during dry etching is deteriorated as described above and hardly dissolves. Therefore, if a strong resist stripping solution capable of stripping a deteriorated resist film is used, the metal wiring (particularly, the copper film) after wet etching will be corroded. On the other hand, if the resist stripping liquid is of such a degree that the metal wiring (copper film) is not corroded, the deteriorated resist film cannot be stripped.
更详细地对以上情况进行说明。链烷醇胺通过亲核作用使作为正型光致抗蚀剂的碱不溶化剂的DNQ化合物的羰基可溶于极性溶剂及水中。The above case will be described in more detail. The alkanolamine makes the carbonyl group of the DNQ compound, which is an alkali insolubilizer of the positive photoresist, soluble in polar solvents and water by nucleophilic action.
通常胺根据键合在氮上的取代基的数量被分为伯、仲、叔。其中，级数越小，碱性越强，亲核性也越强。因此，对于链烷醇胺，越是级数小的链烷醇胺，使作为正型光致抗蚀剂的碱不溶化剂的DNQ化合物可溶于极性溶剂、水中的能力越强，越具有强力的抗蚀剂剥离力。Amines are generally classified as primary, secondary, or tertiary according to the number of substituents bonded to the nitrogen. Among them, the smaller the order, the stronger the basicity and the stronger the nucleophilicity. Therefore, for alkanolamines, the smaller the number of alkanolamines, the stronger the ability to dissolve the DNQ compound as the alkali insolubilizer of the positive photoresist in polar solvents and water, and the more effective it is. Strong resist stripping force.
另一方面，链烷醇胺对铜有螯合作用，其通过形成络合物来腐蚀铜。这种对铜的螯合作用与碱性、亲核性同样地级数越小越强，越腐蚀铜。但是，对铝不发挥该螯合作用，即使为级数少的胺，铝也不被腐蚀。Alkanolamines, on the other hand, have a chelating effect on copper, which corrodes copper by forming complexes. This chelation to copper is the same as basicity and nucleophilicity, the smaller the order, the stronger it is, and the more it corrodes copper. However, this chelating effect is not exerted on aluminum, and aluminum is not corroded even with a small number of amines.
但是考虑到，对于能够剥离变质的抗蚀膜且不腐蚀铜膜的基底的抗蚀剂剥离液，即使基底为铝膜，腐蚀也少。这启示可以将抗蚀剂剥离工序包括抗蚀剂剥离液在内进行一元化。However, it is considered that a resist stripping solution that can peel off a deteriorated resist film without corroding the base of the copper film has little corrosion even if the base is an aluminum film. This suggests that it is possible to unify the resist stripping process including the resist stripping solution.
需要说明的是，如上所述，作为本发明的抗蚀剂剥离液所剥离的对象的抗蚀膜，基底中至少包含铜膜。此外，抗蚀膜可以是经干蚀刻工序的抗蚀膜。需要说明的是，此处，基底是指，包括在剥离抗蚀膜时处于直接暴露于抗蚀剂剥离液的状态的膜。It should be noted that, as described above, the resist film to be stripped by the resist stripping liquid of the present invention includes at least a copper film in the base. In addition, the resist film may be a resist film subjected to a dry etching process. It should be noted that the base here refers to a film that is directly exposed to a resist stripping solution when the resist film is stripped.
如上所述，能够剥离变质的抗蚀膜、且无论基底为铜膜还是铝膜都不被腐蚀的本发明的抗蚀剂剥离液含有链烷醇叔胺、极性溶剂、水以及添加剂。此外，添加剂包含环式胺及糖醇。此外，作为添加剂，也可以是一部分仲胺和糖醇。As described above, the resist stripping solution of the present invention, which can strip a deteriorated resist film and is not corroded regardless of whether the substrate is a copper film or an aluminum film, contains a tertiary alkanol amine, a polar solvent, water, and an additive. In addition, additives include cyclic amines and sugar alcohols. In addition, some secondary amines and sugar alcohols may be used as additives.
作为链烷醇叔胺，具体而言可以适当地利用以下物质。三乙醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二丁基乙醇胺、N-乙基二乙醇胺、N-丁基二乙醇胺、N-甲基二乙醇胺等。这些物质可以混合使用多种。As the tertiary alkanol amine, specifically, the following can be suitably utilized. Triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-methyldiethanolamine Wait. These substances may be used in combination of multiple types.
作为极性溶剂，只要是与水具有亲和性的有机溶剂即可。此外，如果与上述链烷醇叔胺的混合性良好，则更适宜。As the polar solvent, any organic solvent having affinity with water may be used. Moreover, it is more preferable if the miscibility with the above-mentioned tertiary alkanol amine is good.
作为这样的水溶性有机溶剂，可以举出二甲基亚砜等亚砜类；二甲基砜、二乙基砜、双(2-羟乙基)砜、四亚甲基砜等砜类；N,N-二甲基甲酰胺、N-甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基乙酰胺、N,N-二乙基乙酰胺等酰胺类；N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-丙基-2-吡咯烷酮、N-羟甲基-2-吡咯烷酮、N-羟乙基-2-吡咯烷酮等内酰胺类；1,3-二甲基-2-咪唑啉酮、1,3-二乙基-2-咪唑啉酮、1,3-二异丙基-2-咪唑啉酮等咪唑啉酮类；乙二醇、乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丁基醚、乙二醇单甲基醚乙酸酯、乙二醇单乙基醚乙酸酯、二乙二醇、二乙二醇单甲基醚、二乙二醇单乙基醚、二乙二醇单丙基醚、二乙二醇单丁基醚等二乙二醇单烷基醚；丙二醇、丙二醇单甲基醚、丙二醇单乙基醚、丙二醇单丙基醚、丙二醇单丁基醚等丙二醇单烷基醚(烷基为碳原子数1～6的低级烷基)等多元醇类；以及它们的衍生物。这些当中，可以适当地利用选自二甲基亚砜、N-甲基-2-吡咯烷酮、二乙二醇单丁基醚中的至少1种和选自乙二醇、二乙二醇、丙二醇中的至少1种的混合液。其中，对于正型抗蚀剂，利用二乙二醇单丁基醚(BDG)和丙二醇(PG)的混合液作为极性溶剂时，能够得到期望的结果。Examples of such water-soluble organic solvents include sulfoxides such as dimethyl sulfoxide; sulfones such as dimethyl sulfone, diethyl sulfone, bis(2-hydroxyethyl) sulfone, and tetramethylene sulfone; Amides such as N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide; Base-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone and other lactams; 3-Dimethyl-2-imidazolinone, 1,3-diethyl-2-imidazolinone, 1,3-diisopropyl-2-imidazolinone and other imidazolinones; ethylene glycol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether and other diethylene glycol monoalkyl ethers; propylene glycol, propylene glycol mono Polyols such as methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and other propylene glycol monoalkyl ethers (the alkyl group is a lower alkyl group with 1 to 6 carbon atoms); and their derivative. Among these, at least one selected from dimethyl sulfoxide, N-methyl-2-pyrrolidone, and diethylene glycol monobutyl ether, and at least one selected from ethylene glycol, diethylene glycol, and propylene glycol can be suitably used. A mixture of at least one of them. Among them, for the positive resist, when a mixed solution of diethylene glycol monobutyl ether (BDG) and propylene glycol (PG) is used as a polar solvent, desired results can be obtained.
作为添加剂而添加的物质为环式胺或一部分仲胺、及糖醇。作为环式胺，可以举出以下物质。可以适当地利用哌啶、2-甲基哌嗪、N-乙基哌嗪、N-甲基哌嗪、N-氨基乙基哌嗪、2-甲基哌啶、二甲基哌啶、哌嗪、羟基哌嗪、高哌嗪等。即，环式胺中，适宜为具有六元环或七元环结构的环式胺。此外，作为仲胺，至少可以适当地利用N-甲基乙醇胺。Substances added as additives are cyclic amines, some secondary amines, and sugar alcohols. Examples of the cyclic amine include the following. Piperidine, 2-methylpiperazine, N-ethylpiperazine, N-methylpiperazine, N-aminoethylpiperazine, 2-methylpiperidine, dimethylpiperidine, piperidine oxazine, hydroxypiperazine, homopiperazine, etc. That is, among cyclic amines, those having a six-membered ring or seven-membered ring structure are suitable. In addition, at least N-methylethanolamine can be suitably used as the secondary amine.
此外，作为糖醇，可以适当地利用山梨糖醇、木糖醇、蔗糖、甘露糖醇、麦芽糖醇、乳糖醇等。Moreover, as a sugar alcohol, sorbitol, xylitol, sucrose, mannitol, maltitol, lactitol, etc. can be utilized suitably.
如后述的实施例所示，用链烷醇叔胺不能剥离变质的抗蚀膜。另一方面，虽然用仲胺、伯胺能够剥离变质的抗蚀膜，但会腐蚀铜膜。即，为了抑制铜膜的腐蚀，需要考虑将链烷醇叔胺作为主剂。As shown in Examples described later, the deteriorated resist film could not be stripped with tertiary alkanolamines. On the other hand, although the deteriorated resist film can be peeled off with secondary amines and primary amines, the copper film is corroded. That is, in order to suppress the corrosion of the copper film, it is necessary to consider using a tertiary alkanol amine as a main ingredient.
作为添加剂使用环式胺时，抗蚀剂剥离力与添加量成比例地提高。但是，环式胺根据添加量而腐蚀铜膜或铝膜。因此，配混糖醇作为铜膜、铝膜的缓蚀剂。When a cyclic amine is used as an additive, the resist peeling force increases in proportion to the amount added. However, cyclic amines corrode a copper film or an aluminum film depending on the amount added. Therefore, sugar alcohol is compounded as a corrosion inhibitor of copper film and aluminum film.
对于环式胺的添加量，相对于抗蚀剂剥离液总量为0.5～5质量％是适宜的范围。若环式胺的量过多，则铜膜被腐蚀，若过少，则不能剥离干蚀刻后的抗蚀膜。The addition amount of a cyclic amine is an appropriate range of 0.5-5 mass % with respect to the resist stripping liquid whole amount. If the amount of cyclic amine is too large, the copper film will be corroded, and if it is too small, the resist film after dry etching will not be able to be peeled off.
此外，糖醇相对于抗蚀剂剥离液总量适宜为0.5～10质量％。这是因为：由于糖醇具有作为缓蚀剂的作用，因此若过多，则抗蚀膜变得不易剥离。Moreover, sugar alcohol is suitably 0.5-10 mass % with respect to the resist stripping liquid whole quantity. This is because sugar alcohol functions as a corrosion inhibitor, so if it is too large, the resist film will not be easily peeled off.
此外，在本发明的抗蚀剂剥离液中，作为极性溶剂，可以适当地利用二乙二醇单丁基醚(BDG)和丙二醇(PG)的混合液。这些极性溶剂将抗蚀膜溶解，而且使其容易溶解。特别是丙二醇(PG)使抗蚀膜溶胀，二乙二醇单丁基醚(BDG)将抗蚀膜溶解。因此，含有至少2种液体的极性溶剂是有效的。In addition, in the resist stripping solution of the present invention, a mixed solution of diethylene glycol monobutyl ether (BDG) and propylene glycol (PG) can be suitably used as a polar solvent. These polar solvents dissolve the resist film and make it easy to dissolve. In particular, propylene glycol (PG) swells the resist film, and diethylene glycol monobutyl ether (BDG) dissolves the resist film. Therefore, a polar solvent containing at least two liquids is effective.
极性溶剂相对于抗蚀剂剥离液总量适宜为50～80质量％。在使用链烷醇叔胺时，若极性溶剂过多，则pH降低，抗蚀膜的剥离性降低。另一方面，若极性溶剂过少，则抗蚀膜的剥离性仍然降低。The polar solvent is suitably 50-80 mass % with respect to the resist stripping liquid whole quantity. When using a tertiary alkanol amine, if there are too many polar solvents, pH will fall and the stripping property of a resist film will fall. On the other hand, if the polar solvent is too small, the peelability of the resist film will still decrease.
实施例Example
以下示出本发明的抗蚀剂剥离液的实施例及比较例。Examples and comparative examples of the resist stripping liquid of the present invention are shown below.
<抗蚀剂剥离性><Resist stripping property>
从以下两个观点对抗蚀剂剥离性进行评价。The resist peelability was evaluated from the following two viewpoints.
(1)湿蚀刻后的抗蚀剂剥离性(1) Resist stripping property after wet etching
在硅基板上形成100nm的硅热氧化膜，利用溅射法在硅热氧化膜上以300nm的厚度形成铜膜。利用旋转涂布将正型抗蚀液涂布在该铜膜上。抗蚀膜干燥后，用布线图案的掩模进行曝光。然后用抗蚀剂剥离液将感光部分的抗蚀剂剥离。即，为如下状态：具有布线图案的抗蚀膜残留在铜膜上的部分和铜膜露出的部分。A thermally oxidized silicon film of 100 nm was formed on a silicon substrate, and a copper film was formed to a thickness of 300 nm on the thermally oxidized silicon film by sputtering. A positive resist was applied on the copper film by spin coating. After the resist film is dried, exposure is performed using a wiring pattern mask. Then, the resist of the photosensitive portion is stripped with a resist stripping solution. That is, it is in a state where the resist film having the wiring pattern remains on the copper film and where the copper film is exposed.
接着，使用酸系的铜的蚀刻剂，将露出的铜膜蚀刻并去除。铜膜的蚀刻结束后，用样品抗蚀剂剥离液将残留的铜的图案上的抗蚀膜剥离。然后清洗基板，边用光学显微镜施加干涉边观察在铜膜上是否残留有抗蚀膜。在铜膜上确认到抗蚀膜的残留时，记为“×”，没有确认到抗蚀膜的残留时，记为“○”。Next, the exposed copper film is etched and removed using an acid-based copper etchant. After the etching of the copper film was completed, the remaining resist film on the copper pattern was stripped with a sample resist stripping solution. Thereafter, the substrate was cleaned, and it was observed whether or not a resist film remained on the copper film while interfering with an optical microscope. When the remaining of the resist film was confirmed on the copper film, it was described as "x", and when the remaining of the resist film was not confirmed, it was described as "◯".
(2)干蚀刻后的抗蚀剂剥离性(2) Resist stripping property after dry etching
在硅基板上以300nm的厚度形成a-Si(非晶硅)膜。利用旋转涂布将正型抗蚀液涂布在该a-Si膜上。抗蚀膜干燥后，用布线图案的掩模进行曝光。然后用抗蚀剂剥离液将感光部分的抗蚀剂剥离。即，为如下状态：具有在a-Si膜上残留布线图案的抗蚀膜的部分和a-Si膜露出的部分。An a-Si (amorphous silicon) film was formed to a thickness of 300 nm on a silicon substrate. A positive resist solution was applied on this a-Si film by spin coating. After the resist film is dried, exposure is performed using a wiring pattern mask. Then, the resist of the photosensitive portion is stripped with a resist stripping solution. That is, it is in a state where there are portions of the resist film in which the wiring pattern remains on the a-Si film and portions where the a-Si film is exposed.
接着，在真空室中用反应性溅射法将露出的a-Si膜干蚀刻并去除。因此，残留在a-Si膜上的抗蚀膜被暴露于溅射中的等离子体中。a-Si膜的蚀刻结束后，用样品抗蚀剂剥离液将残留的a-Si膜的图案上的抗蚀膜剥离。Next, the exposed a-Si film was dry-etched and removed by reactive sputtering in a vacuum chamber. Therefore, the resist film remaining on the a-Si film is exposed to plasma in sputtering. After the etching of the a-Si film was completed, the remaining resist film on the pattern of the a-Si film was stripped with a sample resist stripping solution.
然后清洗基板，边用光学显微镜施加干涉边观察在a-Si膜上是否残留有抗蚀膜。在a-Si膜上确认到抗蚀膜的残留时，记为“×”，没有确认到抗蚀膜的残留时，记为“○”。Then, the substrate was cleaned, and it was observed whether or not a resist film remained on the a-Si film while interfering with an optical microscope. When the residue of the resist film was confirmed on the a-Si film, it was marked as "×", and when the residue of the resist film was not confirmed, it was marked as "◯".
<基底的腐蚀的程度><The degree of corrosion of the base>
对于基板上制作的铜膜及铝膜，在其上层制作不形成作为绝缘材料的SiNx膜的层。其为格栅线的图案化、a-Si(n+)/a-Si膜的图案化、SD线的图案化、a-Si沟道形成图案化等。在这些图案化时，使用抗蚀剂，为了剥离该抗蚀剂，使用抗蚀剂剥离液。即，抗蚀剂剥离液有时与铜膜及铝膜直接接触。此时，用SEM观测抗蚀剂剥离液腐蚀铜膜及铝膜的程度。A layer in which no SiNx film as an insulating material is formed is formed on top of the copper film and the aluminum film formed on the substrate. It is patterning of grid lines, patterning of a-Si(n+)/a-Si film, patterning of SD lines, patterning of a-Si channel formation, and the like. For these patterning, a resist is used, and a resist stripping solution is used to strip the resist. That is, the resist stripping solution may directly contact the copper film and the aluminum film. At this time, the extent to which the resist stripping solution corroded the copper film and the aluminum film was observed by SEM.
作为基底膜，准备以下3种。As basement membranes, the following three types were prepared.
(1)在硅基板上形成100nm的硅热氧化膜，通过溅射法在硅热氧化膜上形成300nm的铜膜而得到。表中记为“Cu格栅”。(1) A silicon thermal oxide film of 100 nm is formed on a silicon substrate, and a copper film of 300 nm is formed on the silicon thermal oxide film by a sputtering method. It is described as "Cu grid" in the table.
(2)在硅基板上形成100nm的硅热氧化膜，通过溅射法在硅热氧化膜上形成20nm的钼膜后，进而层叠300nm的铜膜而得到。表中记为“Cu/Mo格栅”。钼是用于提高基板与铜膜的粘接力的锚固层。铜膜为该2层结构时，即使抗蚀剂剥离液腐蚀钼层，铜膜也变得不能使用。(2) A silicon thermal oxide film of 100 nm was formed on a silicon substrate, a 20 nm molybdenum film was formed on the silicon thermal oxide film by a sputtering method, and a copper film of 300 nm was further laminated. It is indicated as "Cu/Mo grid" in the table. Molybdenum is an anchor layer for improving the adhesion between the substrate and the copper film. When the copper film has this two-layer structure, even if the resist stripping solution corrodes the molybdenum layer, the copper film becomes unusable.
(3)在硅基板上形成100nm的硅热氧化膜，通过溅射法在硅热氧化膜上形成300nm的铝膜而得到。表中记为“Al格栅”。(3) A silicon thermal oxide film of 100 nm is formed on a silicon substrate, and an aluminum film of 300 nm is formed on the silicon thermal oxide film by a sputtering method. It is described as "Al grid" in the table.
使这些膜在样品抗蚀剂剥离液中浸渍10分钟后，用SEM观察膜。对于腐蚀的程度，如果是能够用作产品的水平，就记为“○”，如果是不能使用的水平就判定为“×”。After immersing these films in the sample resist stripping solution for 10 minutes, the films were observed by SEM. Regarding the degree of corrosion, if it is a level that can be used as a product, it is judged as "◯", and if it is a level that cannot be used, it is judged as "×".
<样品抗蚀剂剥离液><Sample Resist Stripper>
按照以下的要领制备样品抗蚀剂剥离液。样品抗蚀剂剥离液由胺类、极性溶剂、水以及添加剂构成。A sample resist stripping solution was prepared in the following manner. The sample resist stripping solution consists of amines, polar solvents, water, and additives.
(1)实施例1(1) Embodiment 1
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)22.0质量％Propylene glycol (PG) 22.0% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，使用高哌嗪和山梨糖醇。As additives, homopiperazine and sorbitol are used.
高哌嗪1.0质量％Homopiperazine 1.0% by mass
山梨糖醇1.0质量％Sorbitol 1.0% by mass
将以上物质混合搅拌，制成实施例1的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare the sample resist stripping solution of Example 1.
(2)实施例2(2) Embodiment 2
实施例2与实施例1相比减少了添加剂的量。Compared with Example 1, Example 2 reduces the amount of additives.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂由2种混合而得到。The polar solvent is obtained by mixing two types.
丙二醇(PG)22.2质量％Propylene glycol (PG) 22.2% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，使用高哌嗪和山梨糖醇。As additives, homopiperazine and sorbitol are used.
高哌嗪0.9质量％Homopiperazine 0.9% by mass
山梨糖醇0.9质量％Sorbitol 0.9% by mass
将以上物质混合搅拌，制成实施例2的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare the sample resist stripping solution of Example 2.
(3)实施例3(3) Embodiment 3
实施例3与实施例2相比减少了添加剂山梨糖醇的量。Compared with Example 2, Example 3 reduces the amount of additive sorbitol.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)22.6质量％Propylene glycol (PG) 22.6% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，使用高哌嗪和山梨糖醇。As additives, homopiperazine and sorbitol are used.
高哌嗪0.9质量％Homopiperazine 0.9% by mass
山梨糖醇0.5质量％Sorbitol 0.5% by mass
将以上物质混合搅拌，制成实施例3的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare the sample resist stripping solution of Example 3.
(4)实施例4(4) Embodiment 4
实施例4相对于实施例1至3改变了环式胺的种类。In Example 4, the types of cyclic amines are changed relative to Examples 1 to 3.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)22.2质量％Propylene glycol (PG) 22.2% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，使用哌嗪和山梨糖醇。As additives, piperazine and sorbitol are used.
哌嗪0.9质量％Piperazine 0.9% by mass
山梨糖醇0.9质量％Sorbitol 0.9% by mass
将以上物质混合搅拌，制成实施例4的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare the sample resist stripping solution of Example 4.
(5)实施例5(5) Embodiment 5
实施例5相对于实施例1至4改变了环式胺的种类。In Example 5, the types of cyclic amines were changed relative to Examples 1 to 4.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)21.1质量％Propylene glycol (PG) 21.1% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，使用OH-哌嗪和山梨糖醇。As additives, OH-piperazine and sorbitol are used.
OH-哌嗪2.0质量％OH-piperazine 2.0% by mass
山梨糖醇0.9质量％Sorbitol 0.9% by mass
将以上物质混合搅拌，制成实施例5的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare the sample resist stripping solution of Example 5.
将关于以上的实施例1至5的样品抗蚀剂剥离液组成及关于“抗蚀剂剥离性”和“基底的腐蚀的程度”的结果示于表1。Table 1 shows the composition of the sample resist stripping liquid of Examples 1 to 5 above, and the results of "resist stripping property" and "degree of corrosion of the substrate".
(6)比较例1(6) Comparative Example 1
比较例1为没有添加剂的组成。Comparative Example 1 is a composition without additives.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)24.0质量％Propylene glycol (PG) 24.0% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
将以上物质混合搅拌，制成比较例1的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 1.
(7)比较例2(7) Comparative example 2
比较例2改变了胺的种类。In Comparative Example 2, the type of amine was changed.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N,N-二甲基乙醇胺(DMEA)5.0质量％N,N-Dimethylethanolamine (DMEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)24.0质量％Propylene glycol (PG) 24.0% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
将以上物质混合搅拌，制成比较例2的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 2.
(8)比较例3(8) Comparative Example 3
比较例3改变了胺的种类。In Comparative Example 3, the type of amine was changed.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N,N-二乙基乙醇胺(N-DEEA)5.0质量％N,N-diethylethanolamine (N-DEEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)24.0质量％Propylene glycol (PG) 24.0% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
将以上物质混合搅拌，制成比较例3的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 3.
(9)比较例4(9) Comparative Example 4
比较例4改变了胺的种类。In Comparative Example 4, the type of amine was changed.
作为胺类，使用链烷醇仲胺。As amines, alkanol secondary amines are used.
N-甲基乙醇胺(MMA)5.0质量％N-methylethanolamine (MMA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)24.0质量％Propylene glycol (PG) 24.0% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
将以上物质混合搅拌，制成比较例4的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 4.
(10)比较例5(10) Comparative example 5
比较例5改变了胺的种类。In Comparative Example 5, the type of amine was changed.
作为胺类，使用链烷醇伯胺。As amines, primary alkanol amines are used.
单乙醇胺(MEA)5.0质量％Monoethanolamine (MEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)24.0质量％Propylene glycol (PG) 24.0% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
将以上物质混合搅拌，制成比较例5的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 5.
将关于以上的比较例1至5的样品抗蚀剂剥离液组成及关于“抗蚀剂剥离性”和“基底的腐蚀的程度”的结果示于表2。Table 2 shows the composition of the resist stripping liquid of the samples of Comparative Examples 1 to 5 above, and the results of "resist stripping property" and "degree of corrosion of the substrate".
(11)比较例6(11) Comparative example 6
比较例6在比较例1中加入了添加剂。Comparative Example 6 Additives were added to Comparative Example 1.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂由2种混合而得到。The polar solvent is obtained by mixing two types.
丙二醇(PG)23.6质量％Propylene glycol (PG) 23.6% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，加入哌嗪。As an additive, piperazine was added.
哌嗪0.4质量％0.4% by mass of piperazine
将以上物质混合搅拌，制成比较例6的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 6.
(12)比较例7(12) Comparative Example 7
比较例7增加了比较例6的添加剂的量。In Comparative Example 7, the amount of the additive of Comparative Example 6 was increased.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)23.1质量％Propylene glycol (PG) 23.1% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，加入哌嗪。As an additive, piperazine was added.
哌嗪0.9质量％Piperazine 0.9% by mass
将以上物质混合搅拌，制成比较例7的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 7.
(13)比较例8(13) Comparative example 8
比较例8改变了比较例6的添加剂的种类，并且还增加了量。Comparative Example 8 changed the kind of additives of Comparative Example 6, and also increased the amount.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)23.0质量％Propylene glycol (PG) 23.0% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，加入羟乙基哌嗪(表示为“OH-哌嗪”)。As an additive, hydroxyethylpiperazine (indicated as "OH-piperazine") was added.
OH-哌嗪1.0质量％OH-piperazine 1.0% by mass
将以上物质混合搅拌，制成比较例8的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 8.
(14)比较例9(14) Comparative example 9
比较例9增加了比较例8的添加剂的量。Comparative Example 9 increased the amount of additives of Comparative Example 8.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)21.6质量％Propylene glycol (PG) 21.6% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，加入OH-哌嗪。As an additive, OH-piperazine was added.
OH-哌嗪2.4质量％OH-piperazine 2.4% by mass
将以上物质混合搅拌，制成比较例9的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 9.
(15)比较例10(15) Comparative Example 10
比较例10改变了比较例6的添加剂的种类，并且还增加了量。Comparative Example 10 changed the kind of additives of Comparative Example 6, and also increased the amount.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)23.0质量％Propylene glycol (PG) 23.0% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，加入高哌嗪。As an additive, homopiperazine is added.
高哌嗪1.0质量％Homopiperazine 1.0% by mass
将以上物质混合搅拌，制成比较例10的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 10.
(16)比较例11(16) Comparative Example 11
比较例11减少了比较例10的添加剂的量。In Comparative Example 11, the amount of the additive of Comparative Example 10 was reduced.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)23.1质量％Propylene glycol (PG) 23.1% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，加入高哌嗪。As an additive, homopiperazine is added.
高哌嗪0.9质量％Homopiperazine 0.9% by mass
将以上物质混合搅拌，制成比较例11的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 11.
(17)比较例12(17) Comparative Example 12
比较例12减少了比较例11的添加剂的量。In Comparative Example 12, the amount of the additive of Comparative Example 11 was reduced.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)23.3质量％Propylene glycol (PG) 23.3% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，加入高哌嗪。As an additive, homopiperazine is added.
高哌嗪0.7质量％Homopiperazine 0.7% by mass
将以上物质混合搅拌，制成比较例12的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 12.
将关于以上的比较例6至12的样品抗蚀剂剥离液组成及关于“抗蚀剂剥离性”和“基底的腐蚀的程度”的结果示于表3。Table 3 shows the compositions of the resist stripping liquids of the above Comparative Examples 6 to 12 and the results of "resist stripping properties" and "degree of corrosion of the substrate".
参照表1，首先，对于实施例1至5的各样品抗蚀剂剥离液，能够剥离湿蚀刻后的抗蚀膜自不必说，也能够充分剥离被认为干蚀刻时的暴露于等离子体中而变质的、a-Si膜上的干蚀刻后的抗蚀膜。Referring to Table 1, first of all, for each sample resist stripping solution of Examples 1 to 5, it is not only possible to strip the resist film after wet etching, but it is also considered that the resist film exposed to plasma during dry etching can also be fully stripped. Deteriorated, resist film after dry etching on a-Si film.
另一方面，关于基底的腐蚀，对铜膜、钼膜上的铜膜、铝膜中的任意膜进行10分钟的浸渍时，均为能够充分用作产品的程度的腐蚀。即，实施例1至5的各样品抗蚀剂剥离液能够不区分湿蚀刻、干蚀刻地剥离抗蚀膜，并且无论基底为铜膜还是钼膜上的铜膜、还是铝膜，腐蚀的程度都十分低。On the other hand, regarding the corrosion of the base, when any of the copper film, the copper film on the molybdenum film, and the aluminum film was dipped for 10 minutes, it was corroded to a level sufficient for use as a product. That is, each sample resist stripping solution of Examples 1 to 5 can strip the resist film without distinguishing between wet etching and dry etching, and no matter whether the substrate is a copper film, a copper film on a molybdenum film, or an aluminum film, the degree of corrosion Both are very low.
因此，对于实施例1至5的各样品抗蚀剂剥离液，无论基底为铝膜、铜膜还是钼膜上的铜膜，都能够以1种抗蚀剂剥离液进行使用。在此，实施例1至5均为环式胺(哌嗪、羟乙基哌嗪、高哌嗪)与糖醇(山梨糖醇)的组合。Therefore, for each sample resist stripping solution of Examples 1 to 5, regardless of whether the substrate is an aluminum film, a copper film, or a copper film on a molybdenum film, one type of resist stripping solution can be used. Here, Examples 1 to 5 are all combinations of cyclic amines (piperazine, hydroxyethylpiperazine, homopiperazine) and sugar alcohols (sorbitol).
接着参照表2。比较例1至3为使用链烷醇叔胺、完全不含添加剂的样品抗蚀剂剥离液。对于这些组成，虽热基底的腐蚀低，但是不能剥离干蚀刻后的抗蚀膜。Then refer to Table 2. Comparative Examples 1 to 3 are sample resist stripping solutions that use tertiary alkanol amines and do not contain additives at all. With these compositions, although the corrosion of the thermal base was low, the resist film after dry etching could not be peeled off.
比较例4、5减小了胺的级数，使用链烷醇仲胺、链烷醇伯胺。利用这些组成能够剥离干蚀刻后的抗蚀膜。但是，铜膜及钼膜上的铜膜受到不能用作产品的程度的腐蚀。即，越是级数少的胺，剥离抗蚀膜的作用越强，同时也腐蚀基底(特别是铜膜)。认为这是因为在胺和铜膜之间形成有络合物。需要说明的是，铝膜不易形成络合物，即使用级数小的胺，也不被腐蚀。In Comparative Examples 4 and 5, the number of stages of amines was reduced, and alkanol secondary amines and alkanol primary amines were used. With these compositions, the resist film after dry etching can be stripped. However, the copper film on the copper film and the copper film on the molybdenum film were corroded to such an extent that it could not be used as a product. That is, the smaller the number of amines, the stronger the effect of stripping the resist film, and at the same time it corrodes the substrate (especially the copper film). This is considered to be because a complex was formed between the amine and the copper film. It should be noted that the aluminum film is not easy to form a complex, even if the amine with a small order number is used, it will not be corroded.
接着参照表3。对于比较例6至12，为了保持将基底的腐蚀抑制得较低的状态下确保干蚀刻后的抗蚀膜的剥离性，对添加剂进行了研究。哌嗪为环式胺，虽然作为添加剂，但对于抗蚀膜，能够期待与添加级数低的胺同样的效果。此外，由于具有环式这种立体结构，因此也可以期待如下效果：阻碍被认为形成在铜与胺之间的络合物的形成。Then refer to Table 3. In Comparative Examples 6 to 12, additives were examined in order to secure the stripping properties of the resist film after dry etching while keeping the corrosion of the substrate low. Piperazine is a cyclic amine, and although it is used as an additive, the same effect as that of an amine with a low addition order can be expected for the resist film. In addition, since it has a three-dimensional structure such as a ring, an effect of inhibiting the formation of a complex thought to be formed between copper and amine can also be expected.
从仅使用哌嗪作为添加剂的比较例6及7来看，根据哌嗪的含量，能够剥离干蚀刻后的抗蚀膜，与其相反，基底被腐蚀。From Comparative Examples 6 and 7 in which only piperazine was used as an additive, depending on the content of piperazine, the resist film after dry etching could be peeled off, but on the contrary, the substrate was corroded.
比较例8及9为仅使用OH-哌嗪作为添加剂的情况下的结果。通过增加OH-哌嗪的添加量，也能够剥离干蚀刻后的抗蚀膜，但与其一起基底也被腐蚀。Comparative Examples 8 and 9 are the results of using only OH-piperazine as an additive. By increasing the added amount of OH-piperazine, the resist film after dry etching can also be stripped, but the substrate is also corroded along with it.
比较例10至12为仅使用高哌嗪作为添加剂的情况。高哌嗪为0.9质量％到1.0质量％程度时能够剥离干蚀刻后的抗蚀膜。但是，在基底为铝膜的情况下观察到腐蚀。Comparative Examples 10 to 12 are cases where only homopiperazine was used as an additive. When the content of homopiperazine is about 0.9% by mass to 1.0% by mass, the resist film after dry etching can be stripped. However, corrosion was observed in the case where the substrate was an aluminum film.
根据上述，通过以几质量％程度含有环式胺，能够剥离不易剥离的干蚀刻后的抗蚀膜。但是，与此同时，也腐蚀铜膜、铝膜。然而，通过同时添加几质量％程度的糖醇，能够同时实现抗蚀膜的剥离性和铜膜(包括钼膜/铜膜)及铝膜的腐蚀抑制。From the above, by containing a cyclic amine in an amount of about several mass %, the resist film after dry etching which is difficult to peel off can be peeled off. However, at the same time, the copper film and the aluminum film are also corroded. However, by simultaneously adding a sugar alcohol of the order of several mass %, it is possible to simultaneously realize the peelability of the resist film and the corrosion inhibition of the copper film (including the molybdenum film/copper film) and the aluminum film.
如上所述，本发明的抗蚀剂剥离液通过使环式胺和糖醇同时存在，无论基底为铜膜还是铝膜，对抗蚀膜自不必说，即使是对暴露于干蚀刻工序的等离子体中而变质的抗蚀膜，也能够在将基底的腐蚀抑制为较低的同时进行剥离。As described above, the resist stripping solution of the present invention allows the simultaneous presence of cyclic amine and sugar alcohol, regardless of whether the base is a copper film or an aluminum film, it is not only against the resist film, but also against the plasma exposed to the dry etching process. Even a moderately deteriorated resist film can be stripped while suppressing the corrosion of the base to a low level.
接着，示出实施例和比较例，对使用链烷醇仲胺作为添加剂的情况进行说明。Next, examples and comparative examples are shown, and a case where a secondary alkanol amine is used as an additive will be described.
(18)实施例21(18) Example 21
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)21.7质量％Propylene glycol (PG) 21.7% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，使用N-甲基乙醇胺(MMA)和山梨糖醇。As additives, N-methylethanolamine (MMA) and sorbitol were used.
MMA1.4质量％MMA1.4% by mass
山梨糖醇0.9质量％Sorbitol 0.9% by mass
将以上物质混合搅拌，制成实施例21的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Example 21.
(19)比较例21(19) Comparative Example 21
比较例21减少了实施例21的MMA的量。Comparative Example 21 reduced the amount of MMA of Example 21.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)22.2质量％Propylene glycol (PG) 22.2% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，使用N-甲基乙醇胺(MMA)和山梨糖醇。As additives, N-methylethanolamine (MMA) and sorbitol were used.
MMA0.9质量％MMA0.9% by mass
山梨糖醇0.9质量％Sorbitol 0.9% by mass
将以上物质混合搅拌，制成比较例21的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 21.
(20)比较例22(20) Comparative Example 22
比较例22增加了比较例21的MMA的量。In Comparative Example 22, the amount of MMA of Comparative Example 21 was increased.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)21.9质量％Propylene glycol (PG) 21.9% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，使用N-甲基乙醇胺(MMA)和山梨糖醇。As additives, N-methylethanolamine (MMA) and sorbitol were used.
MMA1.2质量％MMA1.2% by mass
山梨糖醇0.9质量％Sorbitol 0.9% by mass
将以上物质混合搅拌，制成比较例22的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 22.
(21)比较例23(21) Comparative Example 23
比较例23增加了比较例22的MMA的量。In Comparative Example 23, the amount of MMA of Comparative Example 22 was increased.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)21.8质量％Propylene glycol (PG) 21.8% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，使用N-甲基乙醇胺(MMA)和山梨糖醇。As additives, N-methylethanolamine (MMA) and sorbitol were used.
MMA1.3质量％MMA1.3% by mass
山梨糖醇0.9质量％Sorbitol 0.9% by mass
将以上物质混合搅拌，制成比较例23的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 23.
将关于以上的实施例21及比较例21至23的样品抗蚀剂剥离液组成及关于“抗蚀剂剥离性”和“基底的腐蚀的程度”的结果示于表4。Table 4 shows the composition of the resist stripping liquid of the above-mentioned Example 21 and Comparative Examples 21 to 23, and the results of "resist stripping property" and "degree of corrosion of the substrate".
(22)比较例24(22) Comparative Example 24
比较例24从实施例21中删除了山梨糖醇。Comparative Example 24 has sorbitol removed from Example 21.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)22.6质量％Propylene glycol (PG) 22.6% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，仅使用N-甲基乙醇胺(MMA)。As additive, only N-methylethanolamine (MMA) was used.
MMA1.4质量％MMA1.4% by mass
将以上物质混合搅拌，制成比较例24的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 24.
(23)比较例25(23) Comparative Example 25
比较例25将比较例24的添加剂改变为N-乙基乙醇胺(MEM)并且还增加了量。Comparative Example 25 changed the additive of Comparative Example 24 to N-ethylethanolamine (MEM) and also increased the amount.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)22.4质量％Propylene glycol (PG) 22.4% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，仅使用N-乙基乙醇胺(MEM)。As an additive, only N-ethylethanolamine (MEM) was used.
MEM1.6质量％MEM1.6% by mass
将以上物质混合搅拌，制成比较例25的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 25.
(24)比较例26(24) Comparative Example 26
比较例26将比较例24的添加剂改变为N-正丁基乙醇胺(MBM)并且还增加了量。Comparative Example 26 changed the additive of Comparative Example 24 to N-n-butylethanolamine (MBM) and also increased the amount.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)21.9质量％Propylene glycol (PG) 21.9% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，仅使用N-正丁基乙醇胺(MBM)。As additive, only N-n-butylethanolamine (MBM) was used.
MBM2.1质量％MBM2.1 mass%
将以上物质混合搅拌，制成比较例26的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 26.
(25)比较例27(25) Comparative Example 27
比较例27将比较例24的添加剂改变为二乙醇胺(DEA)并且还增加了量。Comparative Example 27 changed the additive of Comparative Example 24 to diethanolamine (DEA) and also increased the amount.
作为胺类，使用链烷醇叔胺。As amines, tertiary alkanol amines are used.
N-甲基二乙醇胺(MDEA)5.0质量％N-methyldiethanolamine (MDEA) 5.0% by mass
极性溶剂混合2种。Two kinds of polar solvents are mixed.
丙二醇(PG)22.1质量％Propylene glycol (PG) 22.1% by mass
二乙二醇单丁基醚(BDG)40.0质量％Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水31.0质量％Water 31.0% by mass
作为添加剂，仅使用二乙醇胺(DEA)。As an additive, only diethanolamine (DEA) was used.
DEA1.9质量％DEA1.9% by mass
将以上物质混合搅拌，制成比较例27的样品抗蚀剂剥离液。The above substances were mixed and stirred to prepare a sample resist stripping solution of Comparative Example 27.
将关于以上的比较例24至27的样品抗蚀剂剥离液组成及关于“抗蚀剂剥离性”和“基底的腐蚀的程度”的结果示于表5。Table 5 shows the compositions of the resist stripping liquids of the above Comparative Examples 24 to 27 and the results of "resist stripping properties" and "degree of corrosion of the substrate".
参照表4，对于本发明的实施例21的样品抗蚀剂剥离液，能够剥离湿蚀刻后的抗蚀膜自不必说，还能够充分剥离被认为干蚀刻时的暴露于等离子体中而变质的、a-Si膜上的干蚀刻后的抗蚀膜。Referring to Table 4, the sample resist stripping solution of Example 21 of the present invention can strip not only the resist film after wet etching, but also fully strip the resist film that is considered to be deteriorated by exposure to plasma during dry etching. , A resist film after dry etching on the a-Si film.
此外，参照实施例21及比较例21至23，作为添加剂而使用的链烷醇仲胺的MMA为1.3质量％以下的含量时不能剥离干蚀刻后的抗蚀膜。因此可知，需要相对于抗蚀剂剥离液总量为1.4质量％以上。与此相对，如比较例4中所示，若使MMA相对于抗蚀剂剥离液总量含有5.0质量％，则会腐蚀铜膜。因此，可以说MMA的含量上限为相对于抗蚀剂剥离液总量小于5.0质量％。In addition, referring to Example 21 and Comparative Examples 21 to 23, when the MMA content of the secondary alkanol amine used as an additive was 1.3% by mass or less, the resist film after dry etching could not be peeled off. Therefore, it turns out that it needs to be 1.4 mass % or more with respect to the resist stripping liquid whole amount. On the other hand, as shown in Comparative Example 4, when MMA was contained in an amount of 5.0% by mass relative to the total amount of the resist stripping liquid, the copper film was corroded. Therefore, it can be said that the upper limit of the content of MMA is less than 5.0% by mass relative to the total amount of the resist stripping liquid.
表5中示出添加剂中不含山梨糖醇的组成的结果。若不含山梨糖醇，则即使在作为添加剂使用的情况下，链烷醇仲胺也腐蚀铜膜(参照比较例24)。另一方面，对于MEM、MBM、DEA，虽然为链烷醇仲胺，但即使尝试作为添加剂来含有，也不能去除干蚀刻后的抗蚀膜。Table 5 shows the results of compositions in which sorbitol is not included in the additive. When sorbitol is not contained, the secondary alkanol amine corrodes the copper film even when used as an additive (see Comparative Example 24). On the other hand, although MEM, MBM, and DEA are alkanol secondary amines, even if they are contained as additives, the resist film after dry etching cannot be removed.
因此可以说，直链型的仲胺也能够达到本发明的目的，即发挥不腐蚀铜膜等并且能够剥离变质的抗蚀膜的这种效果，这限定于一部分仲胺。Therefore, it can be said that linear secondary amines can also achieve the object of the present invention, that is, the effect of not corroding copper films and the like and being able to peel off deteriorated resist films, but this is limited to some secondary amines.
如上所述，作为添加剂，通过使链烷醇仲胺的N-甲基乙醇胺(MMA)与糖醇同时存在，无论基底为铜膜还是铝膜，对抗蚀膜自不必说，即使是暴露于干蚀刻工序的等离子体中而变质的抗蚀膜，也能够在将基底的腐蚀抑制为较低的同时进行剥离。As described above, by making N-methylethanolamine (MMA) which is a secondary alkanol amine and sugar alcohol exist together as an additive, it is not necessary to resist the resist film regardless of whether the substrate is a copper film or an aluminum film, even when exposed to dryness. The resist film degraded by the plasma in the etching process can also be stripped while suppressing the corrosion of the base to a low level.
产业上的可利用性Industrial availability
本发明的抗蚀剂剥离液能够适当地用作使用了正型抗蚀剂时的抗蚀剂剥离液。其通常能够适当地用于液晶显示器、等离子体显示器、有机EL等FPD的制造。The resist stripping solution of the present invention can be suitably used as a resist stripping solution when a positive resist is used. Generally, it can be suitably used for manufacture of FPDs, such as a liquid crystal display, a plasma display, and an organic EL.
Claims (12)
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| CN201610810602.2A CN106200283B (en) | 2013-09-02 | 2014-02-17 | Anticorrosive additive stripping liquid controlling |
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| JP2013-190455 | 2013-09-13 | ||
| JP2013190455A JP5575318B1 (en) | 2013-09-02 | 2013-09-13 | Resist stripper |
| PCT/JP2014/000786 WO2015029277A1 (en) | 2013-09-02 | 2014-02-17 | Resist remover liquid |
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| CN201610810602.2A Division CN106200283B (en) | 2013-09-02 | 2014-02-17 | Anticorrosive additive stripping liquid controlling |
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| CN105723284A true CN105723284A (en) | 2016-06-29 |
| CN105723284B CN105723284B (en) | 2017-10-03 |
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| CN201610810602.2A Active CN106200283B (en) | 2013-09-02 | 2014-02-17 | Anticorrosive additive stripping liquid controlling |
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| CN201610810602.2A Active CN106200283B (en) | 2013-09-02 | 2014-02-17 | Anticorrosive additive stripping liquid controlling |
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|---|---|
| JP (2) | JP5575318B1 (en) |
| CN (2) | CN105723284B (en) |
| TW (2) | TWI494712B (en) |
| WO (1) | WO2015029277A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107995960A (en) * | 2016-09-30 | 2018-05-04 | 松下知识产权经营株式会社 | Resist stripper |
| CN112805629A (en) * | 2019-11-20 | 2021-05-14 | 松下知识产权经营株式会社 | Resist stripping liquid |
| CN113614646A (en) * | 2019-03-25 | 2021-11-05 | 松下知识产权经营株式会社 | Resist stripping liquid |
| CN115039036A (en) * | 2020-09-22 | 2022-09-09 | 株式会社Lg化学 | Stripper composition for removing photoresist and method of stripping photoresist using the same |
| CN115167083A (en) * | 2022-07-19 | 2022-10-11 | 深圳深骏微电子材料有限公司 | Aqueous stripping liquid and application thereof |
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| JP5885041B1 (en) * | 2014-10-27 | 2016-03-15 | パナソニックＩｐマネジメント株式会社 | Resist stripper |
| JP5885043B1 (en) * | 2014-12-05 | 2016-03-15 | パナソニックＩｐマネジメント株式会社 | Resist stripper and method for producing the same |
| JP5885045B1 (en) * | 2015-01-27 | 2016-03-15 | パナソニックＩｐマネジメント株式会社 | Resist stripper and method for producing the same |
| JP5885046B1 (en) * | 2015-03-24 | 2016-03-15 | パナソニックＩｐマネジメント株式会社 | Resist stripper |
| JP6938937B2 (en) * | 2017-02-10 | 2021-09-22 | 荒川化学工業株式会社 | Remover for rust preventive film |
| CN108941061B (en) * | 2018-05-18 | 2021-02-05 | 中国人民解放军国防科技大学 | Quantitative cleaning device and method for optical components |
| CN109270808A (en) * | 2018-10-25 | 2019-01-25 | 健鼎（湖北）电子有限公司 | A method of removal dry film |
| EP4038173A4 (en) * | 2019-09-30 | 2023-11-01 | Versum Materials US, LLC | PHOTORESIN REMOVER AGENT |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN105723284B (en) | 2017-10-03 |
| TW201447513A (en) | 2014-12-16 |
| WO2015029277A1 (en) | 2015-03-05 |
| JP5593466B1 (en) | 2014-09-24 |
| JP2015064393A (en) | 2015-04-09 |
| TWI494713B (en) | 2015-08-01 |
| JP5575318B1 (en) | 2014-08-20 |
| TW201445264A (en) | 2014-12-01 |
| TWI494712B (en) | 2015-08-01 |
| CN106200283A (en) | 2016-12-07 |
| CN106200283B (en) | 2017-11-03 |
| JP2015064555A (en) | 2015-04-09 |
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