TW201445264A - Photoresist stripping solution - Google Patents
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- TW201445264A TW201445264A TW103123581A TW103123581A TW201445264A TW 201445264 A TW201445264 A TW 201445264A TW 103123581 A TW103123581 A TW 103123581A TW 103123581 A TW103123581 A TW 103123581A TW 201445264 A TW201445264 A TW 201445264A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
Abstract
Description
本發明關於剝離用於液晶、有機電致發光等的顯示器或半導體製造時所使用之光阻的剝離液，更詳細地，關於可去除乾蝕刻中暴露於電漿的光阻、而且對於鋁膜及銅膜也不會實質地腐蝕的光阻剝離液。 The present invention relates to a peeling liquid for peeling off a photoresist used for display or semiconductor manufacturing for liquid crystal, organic electroluminescence, etc., and more particularly, to remove photoresist exposed to plasma in dry etching, and for aluminum film And a photoresist stripping solution in which the copper film does not substantially corrode.
在液晶及有機電致發光(Electro-Luminescence)等的平面顯示器(FPD)的TFT(Thin Film Transistor)製造步驟，為了形成導線，使用經過光微影的蝕刻。 In the TFT (Thin Film Transistor) manufacturing process of a flat panel display (FPD) such as liquid crystal or organic electroluminescence (Electro-Luminescence), etching by photolithography is used in order to form a wire.
使用此蝕刻，在例如已成膜的金屬膜上形成光阻膜。光阻膜透過圖案光罩而曝光、顯影，經蝕刻所殘留的圖案(或其負像圖案)殘存在膜上。之後，以利用電漿等的乾蝕刻去除露出的金屬膜。在乾蝕刻中保護金屬膜而圖案化的光阻膜，之後以光阻剝離液剝離。 Using this etching, a photoresist film is formed on, for example, a film-formed metal film. The photoresist film is exposed and developed through the pattern mask, and the pattern remaining by the etching (or its negative pattern) remains on the film. Thereafter, the exposed metal film is removed by dry etching using plasma or the like. The photoresist film patterned by protecting the metal film in dry etching is then peeled off by the photoresist stripping solution.
習知的導線主要是以鋁所形成。但是，由於FPD的大型化，必須流通大量的電流，因此檢討以電阻率更小的銅做為導線使用。 Conventional wires are mainly formed of aluminum. However, since a large amount of current has to be circulated due to the increase in the size of the FPD, it has been reviewed to use copper having a smaller specific resistance as a wire.
然而，銅在光阻剝離液被腐蝕的情形很多，剝離形成於銅膜上的光阻膜的光阻剝離液必須要使光阻膜剝離，且抑制銅的腐蝕。有提議含有苯併三唑的光阻剝離液作為銅的防腐蝕劑。除此之外，有提議哌嗪(piperazine)的化合物可剝離光 阻且對銅的腐蝕亦小(專利文獻1、專利文獻2)。 However, copper is often corroded in the photoresist stripping solution, and the photoresist stripping liquid which peels off the photoresist film formed on the copper film must peel off the photoresist film and suppress corrosion of copper. A photoresist stripping solution containing benzotriazole is proposed as an anticorrosive agent for copper. In addition, there are proposed compounds for piperazine that can strip light. Corrosion to copper is also suppressed (Patent Document 1 and Patent Document 2).
另一方面，在FPD，也有以鋁進行接線的地方，剝離鋁膜上的光阻膜和銅膜上的光阻膜的光阻剝離液，被分別調配。 On the other hand, in the FPD, where the wiring is made of aluminum, the photoresist film on the photoresist film on the aluminum film and the photoresist film on the copper film are separately prepared.
所謂使鋁膜和銅膜上的光阻膜的剝離液共存的課題的提起，可追溯到專利文獻1的時代。專利文獻3揭示，在對鋁和銅選擇性蝕刻時，使提供質子的有機溶劑或接受質子的有機溶劑在室溫以上與剝離對象的光阻膜接觸，放置在氧化劑和水分1000ppm以上的環境的技術。 The problem of coexisting the peeling liquid of the photoresist 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 an organic solvent that supplies a proton or a proton-donating organic solvent is brought into contact with a photoresist film to be peeled off at room temperature or higher, and is placed in an environment of an oxidizing agent and a water content of 1000 ppm or more. .
專利文獻4揭示，剝離銅膜上的光阻膜之光阻剝離液。專利文獻4揭示，含有胺、和溶劑、和強鹼及水的光阻剝離液。專利文獻4以上述組成的光阻剝離液在氧濃度為特定值以下的環境中使用，來防止銅的腐蝕。 Patent Document 4 discloses that the photoresist peeling liquid of the photoresist film on the copper film is peeled off. Patent Document 4 discloses a photoresist stripping solution containing an amine, a solvent, and a strong base and water. Patent Document 4 uses a photoresist stripper having the above composition in an environment where the oxygen concentration is equal to or lower than a specific value to prevent corrosion of copper.
專利文獻5係為了解決經乾蝕刻步驟的光阻膜變質、顯影時在溶液中不易剝離的課題所想到者。其揭示以胺、和醚、和糖醇、和四級胺、和水所構成的光阻剝離液。又專利文獻4係估計光阻膜形成於鋁膜上，並非估計形成於銅上。 Patent Document 5 is intended to solve the problem of deterioration of the photoresist film in the dry etching step and difficulty in peeling off in solution during development. It discloses a photoresist stripper composed of an amine, an ether, and a sugar alcohol, and a quaternary amine, and water. Further, Patent Document 4 estimates that a photoresist film is formed on an aluminum film and is not necessarily formed on copper.
【專利文獻1】日本特開昭60-131535號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 60-131535
【專利文獻2】日本特開2006-079093號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-079093
【專利文獻3】日本特開平05-047654號公報 [Patent Document 3] Japanese Patent Publication No. 05-047654
【專利文獻4】日本特開2003-140364號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2003-140364
【專利文獻5】日本特開平08-262746號公報 [Patent Document 5] Japanese Laid-Open Patent Publication No. 08-262746
雖然專利文獻5也言及，經過乾蝕刻步驟的光阻膜變質而不易剝離。如此，必須使用在如一級胺或二級胺的強鹼下剝離力強的光阻剝離液。 Although Patent Document 5 also mentions that the photoresist film subjected to the dry etching step is deteriorated and is not easily peeled off. Thus, it is necessary to use a photoresist stripping solution having a strong peeling force under a strong base such as a primary amine or a secondary amine.
使用此種剝離力強的光阻剝離液的情形時，當基底為鋁膜時，不會被過度腐蝕。但是，當基底為銅膜時會被腐蝕。此處，基底包含在剝離光阻層時直接暴露於光阻剝離液的狀態的膜。 When such a peeling liquid having a strong peeling force is used, when the substrate is an aluminum film, it is not excessively corroded. However, when the substrate is a copper film, it is corroded. Here, the substrate includes a film that is directly exposed to the photoresist stripping liquid when the photoresist layer is peeled off.
亦即，一級胺或二級胺可使在正型光阻所使用的由酚醛樹脂和難溶於鹼的重氮萘醌(diazonaphthoquinone)化合物溶解於極性溶劑或水，也會使銅溶解。 That is, the primary or secondary amine can dissolve the phenolic resin and the diazonaphthoquinone compound which is poorly soluble in the base in a polar solvent or water, and also dissolve the copper.
因此，目前以銅為基底的情形，剝離經過乾蝕刻步驟的光阻膜時，使用灰化等技術，在去除特定膜厚的光阻膜後使用光阻剝離液。 Therefore, in the case where copper is used as the base, when the photoresist film subjected to the dry etching step is peeled off, a photoresist peeling liquid is used after removing the photoresist film having a specific film thickness by using a technique such as ashing.
在FPD的製造中，存在使用銅膜的製品和使用鋁膜的製品。因此，如果可以使用1種光阻剝離液使在鋁和銅上形成的光阻膜剝離，則可使剝離製程線成為1個。又因為也可使光阻剝離液的管理一元化，不只製造流程上非常可取，也有助於成本的削減。 In the manufacture of FPD, there are articles using a copper film and articles using an aluminum film. Therefore, if the photoresist film formed on aluminum and copper can be peeled off using one type of photoresist stripping liquid, the peeling process line can be made one. Moreover, since the management of the photoresist stripping liquid can be unified, it is not only highly desirable in the manufacturing process, but also contributes to cost reduction.
專利文獻1、2提及提供使在蝕刻步驟變質而不易剝離的光阻剝離、且不腐蝕金屬接線的光阻剝離液。然而，實際上，沒有確認改變基底的金屬種類時的剝離性及腐蝕性。 Patent Documents 1 and 2 mention that a photoresist stripping liquid which peels off a photoresist which is deteriorated in an etching step and is not easily peeled off, and which does not corrode a metal wiring is provided. However, in actuality, peelability and corrosivity at the time of changing the metal type of the base were not confirmed.
專利文獻3為對於鋁和銅同時存在的狀態下剝離光阻的發明。但是，只有記載具有烷基苯磺酸的有機溶劑作為提供質子的有機溶劑、含有單乙醇胺的剝離液作為接受質子的有機溶劑，沒有具體的組成的揭示。 Patent Document 3 is an invention in which a photoresist is peeled off in a state in which aluminum and copper are simultaneously present. However, only an organic solvent having an alkylbenzenesulfonic acid is described as an organic solvent for supplying protons and a stripping solution containing monoethanolamine as an organic solvent for accepting protons, and no specific composition is disclosed.
專利文獻4提及銅膜上的光阻膜的剝離，但沒有提及可以和鋁膜上的光阻膜剝離液共用。 Patent Document 4 mentions the peeling of the photoresist film on the copper film, but does not mention that it can be shared with the photoresist film stripping liquid on the aluminum film.
因此，沒有提議可使以電漿變質的光阻膜剝離、且基底即使為銅膜、即使為鋁膜、也實質地不腐蝕的光阻剝離液。 Therefore, there is no proposal for a photoresist stripping liquid which can be peeled off by plasma deterioration, and which is a copper film and a substantially non-corrosive even if it is an aluminum film.
本發明為鑑於上述課題所想到，提供可使在乾蝕刻時暴露於電漿、變質的光阻膜剝離、且基底即使為鋁膜、即使為銅膜、也實質上不產生問題地減少腐蝕的光阻剝離液。 In view of the above-described problems, the present invention provides a photoresist film which can be exposed to plasma and deteriorated during dry etching, and which has an aluminum film and a copper film, which does not cause any problem to reduce corrosion. Photoresist stripper.
更具體地，本發明所述之光阻剝離液是以包含三級烷醇胺、和極性溶劑、和水、和環胺、和糖醇為特徵。又，也可使用一部分的二級胺替代環胺。 More specifically, the photoresist stripping solution of the present invention is characterized by comprising a tertiary alkanolamine, and a polar solvent, and water, a cyclic amine, and a sugar alcohol. Alternatively, a portion of the secondary amine may be used in place of the cyclic amine.
本發明所述的光阻剝離液可使乾蝕刻時暴露於電漿而變質的光阻膜剝離。另一方面，提供基底即使為銅膜、即使為鋁膜、實質上可允許的腐蝕程度之光阻剝離液。 The photoresist stripping liquid of the present invention can peel off the photoresist film which is deteriorated by exposure to plasma during dry etching. On the other hand, a photoresist peeling liquid having a substrate of a copper film and even an aluminum film and a substantially acceptable degree of corrosion is provided.
因此，即使是鋁膜上的光阻膜、即使是銅膜上的光阻膜，可以使用1種光阻剝離液剝離。因此，光阻膜的剝離製程線不必有複數種，光阻剝離液也可以是1種的管理。所謂的灰化步驟也不需要。結果有助於提高工廠的生產性和成本的 降低。 Therefore, even a photoresist film on an aluminum film or even a photoresist film on a copper film can be peeled off using one type of photoresist peeling liquid. Therefore, the stripping process line of the photoresist film does not have to be plural, and the photoresist stripping liquid may be one type of management. The so-called ashing step is also not required. The results help to increase the productivity and cost of the plant reduce.
以下對於本發明所述之光阻剝離液進行說明。又以下說明係顯示本發明所述光阻剝離液的一實施型態，在不脫離本發明旨趣的範圍內，下述的實施型態和實施例也可以變化。 The photoresist stripping liquid of the present invention will be described below. Further, the following description shows an embodiment of the resist stripping liquid of the present invention, and the following embodiments and examples can be changed without departing from the scope of the present invention.
本發明所述之光阻剝離液所剝離的光阻膜估計為正型光阻。正型光阻使用含有酚醛系樹脂作為樹脂、重氮萘醌(以下記為「DNQ」)化合物作為感光劑。進行蝕刻的情形，係在基板上形成光阻膜，中間介有圖案而進行曝光。 The photoresist film from which the photoresist stripping liquid of the present invention is peeled off is estimated to be a positive photoresist. As the positive resist, a phenolic resin is used as a resin, and a compound of diazonaphthoquinone (hereinafter referred to as "DNQ") is used as a sensitizer. In the case of etching, a photoresist film is formed on a substrate, and a pattern is interposed to expose the film.
經由此曝光，DNQ化合物變為烯酮(indene ketene)。烯酮和水接觸，轉變為烯羧酸(indene carboxylic acid)，溶解於水。酚醛系的樹脂基本上具有溶解於鹼性溶液的性質，但是因DNQ而使溶解點被保護。DNQ因曝光而變質，在水中開始溶化，酚醛樹脂也溶出。如此完成光阻膜的圖案化。 Upon this exposure, the DNQ compound becomes an indenene ketene. The ketene is contacted with water, converted to an indenene carboxylic acid, and dissolved in water. The phenolic resin basically has a property of being dissolved in an alkaline solution, but the dissolution point is protected by DNQ. DNQ deteriorates due to exposure, begins to dissolve in water, and phenolic resin also dissolves. The patterning of the photoresist film is thus completed.
經由光阻膜而完成圖案化的基板，進行濕蝕刻或乾蝕刻的處理。乾蝕刻為在真空中進行的處理，作為圖案而殘存的光阻膜暴露於高溫和自由基的氛圍氣。如此，光阻膜中的酚醛系樹脂彼此再結合，變質為難以溶解的組成。 The patterned substrate is completed through a photoresist film, and subjected to wet etching or dry etching. The dry etching is a treatment performed in a vacuum, and the photoresist film remaining as a pattern is exposed to a high temperature and a free radical atmosphere. As described above, the phenolic resins in the photoresist film recombine with each other and deteriorate into a composition that is difficult to dissolve.
由於蝕刻後不需要光阻膜，以光阻剝離液剝離。亦即，光阻剝離液所剝離的光阻膜，經過乾蝕刻步驟的光阻膜也成為對象。而且，基板上殘存的光阻膜雖然沒有經過曝光步驟，但在蝕刻結束後暴露於電漿或放置螢光燈下，光阻膜全部為曝光的狀態。 Since the photoresist film is not required after the etching, the photoresist stripping solution is peeled off. That is, the photoresist film which is peeled off by the photoresist stripping liquid is also a target of the photoresist film which has undergone the dry etching process. Further, although the photoresist film remaining on the substrate is not subjected to the exposure step, after the etching is completed, it is exposed to the plasma or the fluorescent lamp is placed, and the photoresist film is entirely exposed.
光阻剝離液成為問題的局面為如下述的局面。例如，以製作FET(Field Effect Transistor)的基本流程說明。基板上以銅或鋁使閘極等接線圖案化。此經過以濕蝕刻去除銅或鋁的步驟。此時，殘存於銅或鋁上的光阻，可以光阻剝離液去除。此時，銅或鋁經由接觸光阻剝離液而被腐蝕。 The situation in which the photoresist stripping solution is a problem is as follows. For example, a basic flow chart of a FET (Field Effect Transistor) is described. A wiring such as a gate is patterned by copper or aluminum on the substrate. This is followed by a step of removing copper or aluminum by wet etching. At this time, the photoresist remaining on the copper or aluminum can be removed by the photoresist stripping solution. At this time, copper or aluminum is corroded by contacting the photoresist stripping solution.
之後，使銅膜或鋁膜的圖案上形成SiNx層作為絕緣膜，在SiNx層上形成成為半導體部分的a-Si(n+)/a-Si(非晶矽)層。a-Si(n+)/a-Si層塗佈光阻、曝光、顯影，經乾蝕刻進行a-Si(n+)/a-Si層的圖案化。之後以光阻剝離液去除光阻，但進行乾蝕刻時暴露於電漿的光阻膜如上述變質、難以溶解。 Thereafter, a SiNx layer is formed as an insulating film on the pattern of the copper film or the aluminum film, and an a-Si(n+)/a-Si (amorphous germanium) layer serving as a semiconductor portion is formed on the SiNx layer. The a-Si(n+)/a-Si layer was coated with photoresist, exposed, developed, and patterned by a dry etching of the a-Si(n+)/a-Si layer. Thereafter, the photoresist is removed by the photoresist stripping solution, but the photoresist film exposed to the plasma during dry etching is deteriorated as described above and is difficult to dissolve.
然後，在a-Si(n+)/a-Si層上形成SD(源極、汲極)接線用的金屬膜，在金屬膜上塗佈光阻、曝光、顯影，經濕蝕刻進行SD接線的圖案化。之後經由乾蝕刻去除a-Si(n+)層，形成a-Si層的通道。此時也進行乾蝕刻之時，暴露於電漿的光阻膜變質，難以溶解。之後，銅膜或鋁膜的圖案上殘存的光阻膜以光阻剝離液去除。此時銅膜或鋁膜也因和光阻剝離液接觸而受到腐蝕。 Then, a metal film for SD (source, drain) wiring is formed on the a-Si(n+)/a-Si layer, photoresist is applied on the metal film, exposed, developed, and wet-etched for SD wiring. Patterned. The a-Si(n+) layer is then removed by dry etching to form a channel of the a-Si layer. At the time of dry etching, the photoresist film exposed to the plasma is deteriorated and it is difficult to dissolve. Thereafter, the photoresist film remaining on the pattern of the copper film or the aluminum film is removed by the photoresist stripping solution. At this time, the copper film or the aluminum film is also corroded by contact with the resist stripping solution.
進行乾蝕刻之時暴露於電漿的光阻膜如上所述變質而難以溶解。此時，使用類似可剝離變質的光阻膜的強力光阻剝離液，會使得濕蝕刻後的金屬接線(特別是銅膜)受到腐蝕。另一方面，使用不腐蝕金屬接線(銅膜)程度的光阻剝離液，則無法剝離變質的光阻膜。 The photoresist film exposed to the plasma at the time of dry etching is deteriorated as described above and is difficult to dissolve. At this time, the use of a strong photoresist stripper similar to the peelable metamorphic photoresist film causes the metal wiring (especially the copper film) after the wet etching to be corroded. On the other hand, when a photoresist stripping liquid which does not corrode a metal wiring (copper film) is used, the deteriorated photoresist film cannot be peeled off.
更詳細地說明上述內容。烷醇胺因為親核作用，使得正型光阻中難溶於鹼的DNQ化合物的羰基可溶於極性溶 劑或水。 The above content will be explained in more detail. Alkanolamine is carbonyl-soluble in the DNQ compound which is hardly soluble in alkali in the positive resist due to nucleophilic action. Agent or water.
一般而言，胺類根據鍵結於氮的取代基數目，分為一級、二級、三級。這些之中，級數小的鹼性強，親核性也強。因此，即使是烷醇胺，級數小的烷醇胺，會使正型光阻中難溶鹼的DNQ化合物可溶於極性溶劑或水的力量強，具有強的光阻剝離力。 In general, amines are classified into primary, secondary, and tertiary depending on the number of substituents bonded to nitrogen. Among these, the number of stages is small and the base is strong, and the nucleophilicity is also strong. Therefore, even an alkanolamine having a small number of alkanolamines has a strong DNQ compound which is poorly soluble in a positive photoresist and which is soluble in a polar solvent or water, and has a strong photoresist peeling force.
另一方面，烷醇胺對銅具有螯合作用，經由形成錯合物而使銅腐蝕。此述對銅的螯合作用，與鹼性和親核性相同，級數小的對銅的腐蝕強。但是，對鋁不會發揮此種螯合作用，即使是級數小的胺也不會使鋁腐蝕。 On the other hand, alkanolamines have a chelation effect on copper, which corrodes copper by forming a complex. The chelation of copper is the same as that of alkali and nucleophilicity, and the small number of grades is highly corrosive to copper. However, aluminum does not exhibit such chelation, and even an amine having a small number of grades does not corrode aluminum.
然而，考量可以剝離變質的光阻膜、而不腐蝕基底銅膜的光阻剝離液，基底即使是鋁膜也腐蝕少。此暗示在光阻剝離步驟中含有光阻剝離液而可一元化的可能性。 However, it is considered that the photoresist film which can peel off the deteriorated photoresist film without corroding the underlying copper film is less corroded even if the substrate is an aluminum film. This suggests the possibility of including a photoresist stripping solution in the photoresist stripping step to be uniform.
又如上所述，作為本發明所述之光阻剝離液的剝離對象的光阻膜在基底包含至少銅膜。又光阻膜也可為經過乾蝕刻步驟的光阻膜。此處，基底包括在剝離光阻膜時直接暴露於光阻剝離液的狀態的膜。 Further, as described above, the resist film to be peeled off as the photoresist stripping liquid of the present invention contains at least a copper film on the substrate. Further, the photoresist film may be a photoresist film subjected to a dry etching step. Here, the substrate includes a film that is directly exposed to the photoresist stripping liquid when the photoresist film is peeled off.
如上所述，可剝離變質的光阻膜、基底即使是銅膜、即使是鋁膜也不會腐蝕的本發明之光阻剝離液，包含三級烷醇胺、和極性溶劑、和水、和添加劑。添加劑包含環胺及糖醇。又做為添加劑，也可以是一部分的二級胺和糖醇。 As described above, the photoresist film of the present invention which can be peeled off and deteriorated, and the substrate which is not a copper film or an aluminum film, contains a tertiary alkanolamine, a polar solvent, and water, and additive. The additive comprises a cyclic amine and a sugar alcohol. As an additive, it may also be a part of a secondary amine and a sugar alcohol.
三級烷醇胺具體地可適宜利用下述者。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。 這些也可混合複數種使用。 The tertiary alkanolamine can be suitably used as follows. Triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-methyldiethanolamine Wait. These can also be used in combination with a plurality of types.
極性溶劑可為和水有親和性的有機溶劑。如果與上述三級烷醇胺的混合性良好者更加適合。 The polar solvent may be an organic solvent having an affinity for water. It is more suitable if it has good miscibility with the above tertiary alkanolamine.
如此的水溶性有機溶劑可列舉二甲基亞碸(dimethylsulfoxide)等的亞碸類；二甲碸、二乙碸、雙(2-羥乙基)碸、四亞甲基碸等的碸類；N,N-二甲基甲醯胺、N-甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基乙醯胺、N,N-二乙基乙醯胺等的醯胺類；N-甲基-2-吡咯啶(N-methyl-2-pyrrolidone)、N-乙基-2-吡咯啶、N-丙基-2-吡咯啶、N-羥甲基-2-吡咯啶、N-羥乙基-2-吡咯啶等的內醯胺類(lactam)；1,3-二甲基-2-咪唑啉酮、1,3-二乙基-2-咪唑啉酮、1,3-二異丙基-2-咪唑啉酮等的咪唑啉酮類(imidazolidinone)；乙二醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚等的二乙二醇單烷基醚、丙二醇、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等的丙二醇單烷基醚(烷基為碳數1~6的低級烷基)等的多價烷醇類、及其衍生物。這些之中，可適當利用從二甲基亞碸、N-甲基-2-吡咯啶、二乙二醇單丁基醚之中選擇至少1種，和從乙二醇、二乙二醇、丙二醇之中選擇至少1種的混合液。其中，對正型光阻而言，利用二乙二醇單丁基醚(BDG)和丙二醇(PG)的混合液作為極性溶劑時，可得到所希望的結果。 Examples of such a water-soluble organic solvent include an anthracene such as dimethylsulfoxide; an anthraquinone such as dimethylhydrazine, diethyl hydrazine, bis(2-hydroxyethyl)hydrazine or tetramethylene hydrazine; N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide, etc. Amidoxime; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidine, N-propyl-2-pyrrolidine, N-hydroxymethyl-2 - lactam, such as pyrrolidine or N-hydroxyethyl-2-pyrrolidine; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazoline Imidazolidinone such as ketone or 1,3-diisopropyl-2-imidazolidinone; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol single Butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, two Diethylene glycol monoalkyl ether such as ethylene glycol monopropyl ether or diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Butyl ether of propylene glycol monoalkyl ether (the alkyl is a lower alkyl group having a carbon number of 1 to 6) or the like polyvalent alkanols and derivatives thereof. Among these, at least one selected from the group consisting of dimethyl hydrazine, N-methyl-2-pyrrolidine, and diethylene glycol monobutyl ether can be suitably used, and ethylene glycol and diethylene glycol are used. A mixture of at least one of propylene glycol is selected. Among them, in the case of a positive photoresist, 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.
作為添加劑而添加者為環胺或一部分的二級胺、 以及糖醇。環胺可列舉下列者。哌啶(piperidine)、2-甲基哌嗪(2-methyl piperazine)、N-乙基哌嗪、N-甲基哌嗪、N-胺乙基哌嗪、2-哌可酸(2-pipecolic acid)、二甲基哌啶(lupetidine)、哌嗪(piperazine)、羥基哌嗪、高哌嗪(homopiperazine)等可適宜利用。亦即，在環胺中，具有六員環或七員環結構的環胺為宜。又，做為二級胺，至少N-甲基乙醇胺可適宜利用。 The additive is added as a cyclic amine or a part of a secondary amine, And sugar alcohol. The following examples include the cyclic amine. Piperidine, 2-methyl piperazine, N-ethylpiperazine, N-methylpiperazine, N-amine ethylpiperazine, 2-pipecolic acid Acid), lutidine, piperazine, hydroxypiperazine, homopiperazine, and the like can be suitably used. That is, in the cyclic amine, a cyclic amine having a six-membered ring or a seven-membered ring structure is preferred. Further, as the secondary amine, at least N-methylethanolamine can be suitably used.
作為糖醇，山梨糖醇、木醣醇、蔗糖、甘露醇、麥芽糖醇、乳糖醇等可適宜利用。 As the sugar alcohol, sorbitol, xylitol, sucrose, mannitol, maltitol, lactitol or the like can be suitably used.
如後述的實施例所示，三級烷醇胺無法使變質的光阻膜剝離。另一方面，二級胺及一級胺雖然可以使變質的光阻膜剝離，但是會腐蝕銅膜。因此，為了抑制銅膜的腐蝕，有以三級烷醇胺作為主劑的考量的必要。 As shown in the examples described later, the tertiary alkanolamine cannot peel off the deteriorated photoresist film. On the other hand, although the secondary amine and the primary amine can peel off the deteriorated photoresist film, the copper film is corroded. Therefore, in order to suppress the corrosion of the copper film, it is necessary to consider the tertiary alkanolamine as a main component.
使用環胺作為添加劑時，根據添加量而提高光阻剝離力。但是，根據添加量，環胺會腐蝕銅膜或鋁膜。此處，調配糖醇作為銅膜及鋁膜的防腐蝕劑。 When a cyclic amine is used as an additive, the photoresist peeling force is increased according to the amount of addition. However, depending on the amount added, the cyclic amine will corrode the copper film or the aluminum film. Here, sugar alcohol is formulated as an anticorrosive agent for a copper film and an aluminum film.
環胺的添加量，相對於光阻剝離液的全量，以0.5~5質量%為適宜範圍。環胺過多時，銅膜被腐蝕，過少則無法剝離乾蝕刻後的光阻膜。 The amount of the cyclic amine added is preferably in the range of 0.5 to 5% by mass based on the total amount of the resist stripping solution. When the amount of the cyclic amine is too large, the copper film is corroded, and if it is too small, the photoresist film after dry etching cannot be peeled off.
又，糖醇，相對於光阻剝離液的全量，以0.5~10質量%為宜。糖醇由於做為防腐蝕劑的作用，過多會使光阻膜難以剝離。 Further, the sugar alcohol is preferably 0.5 to 10% by mass based on the total amount of the photoresist stripping solution. Since the sugar alcohol acts as an anticorrosive agent, too much will make the photoresist film difficult to peel off.
本發明所述之光阻剝離液可適宜利用二乙二醇單丁基醚(BDG)和丙二醇(PG)的混合液作為極性溶劑。這些極性溶劑溶解、又容易溶解光阻膜。特別是丙二醇(PG)使光阻膜膨 潤，二乙二醇單丁基醚(BDG)使光阻膜溶解。因此，含有至少二液的極性溶劑是有效的。 The photoresist stripping liquid of the present invention can suitably use a mixed solution of diethylene glycol monobutyl ether (BDG) and propylene glycol (PG) as a polar solvent. These polar solvents dissolve and dissolve the photoresist film easily. In particular, propylene glycol (PG) causes the photoresist film to swell Run, diethylene glycol monobutyl ether (BDG) dissolves the photoresist film. Therefore, a polar solvent containing at least two liquids is effective.
極性溶劑，相對於光阻剝離液的全量，以50~80質量%為宜。在使用三級烷醇胺的情形，極性溶劑過多時，pH下降，光阻膜的剝離性降低。另一方面，當極性溶劑過少時，還是光阻膜的剝離性會降低。 The polar solvent is preferably 50 to 80% by mass based on the total amount of the resist stripping solution. In the case of using a tertiary alkanolamine, when the amount of the polar solvent is too large, the pH is lowered, and the peeling property of the photoresist film is lowered. On the other hand, when the polar solvent is too small, the peeling property of the photoresist film is also lowered.
以下顯示本發明所述之光阻剝離液之實施例和比較例。 Examples and comparative examples of the photoresist stripping liquid of the present invention are shown below.
<光阻剝離性> <Photoresistability>
光阻剝離性以下列兩點評估。 The photoresist peelability was evaluated in the following two points.
(1)濕蝕刻後的光阻剝離性 (1) Photoresist peelability after wet etching
在矽基板上形成100nm的矽熱氧化膜，在矽熱氧化膜上以濺鍍法形成厚度300nm的銅膜。在此銅膜上，以旋轉塗佈正型光阻液。光阻膜乾燥後，使用接線圖案的光罩曝光。之後，使用光阻剝離液使感光部分的光阻剝離。最後為，有銅膜上接線圖案的光阻膜殘存的部分和銅膜露出的部分的狀態。 A tantalum oxide film of 100 nm was formed on the tantalum substrate, and a copper film having a thickness of 300 nm was formed by sputtering on the tantalum oxide film. On this copper film, a positive type resist liquid was spin-coated. After the photoresist film is dried, it is exposed using a photomask of the wiring pattern. Thereafter, the photoresist of the photosensitive portion was peeled off using a photoresist stripping solution. Finally, there is a state in which the portion of the photoresist film remaining on the copper film wiring pattern and the portion where the copper film is exposed.
之後，使用酸性的銅蝕刻液，蝕刻、除去露出的銅膜。在銅膜的蝕刻結束後，殘存的銅的圖案上的光阻膜，使用樣品光阻剝離液剝離。之後，洗淨基板，以光學顯微鏡一邊干涉一邊觀察銅膜上是否殘留光阻膜。被辨認出銅膜上光阻膜的殘留時，標記為「×」，未辨認出光阻膜的殘留時，標記為「○」。 Thereafter, the exposed copper film was etched and removed using an acidic copper etching solution. After the etching of the copper film is completed, the photoresist film on the remaining copper pattern is peeled off using the sample photoresist stripper. Thereafter, the substrate was washed, and the photoresist film was left on the copper film while interfering with the optical microscope. When the residue of the photoresist film on the copper film is recognized, it is marked as "x", and when the photoresist film remains unrecognized, it is marked as "○".
(2)乾蝕刻後的光阻剝離性 (2) Photoresist stripping after dry etching
矽基板上形成厚度300nm的a-Si(非晶矽)膜。在該a-Si膜上以旋轉塗佈正型光阻液。光阻膜乾燥後，使用接線圖案的光罩曝光。之後，使用光阻剝離液使感光部分的光阻剝離。最後為，有a-Si膜上接線圖案的光阻膜殘存的部分和a-Si膜露出的部分的狀態。 An a-Si (amorphous germanium) film having a thickness of 300 nm was formed on the germanium substrate. A positive photoresist liquid was spin-coated on the a-Si film. After the photoresist film is dried, it is exposed using a photomask of the wiring pattern. Thereafter, the photoresist of the photosensitive portion was peeled off using a photoresist stripping solution. Finally, the state in which the portion of the photoresist film remaining on the wiring pattern of the a-Si film and the portion where the a-Si film is exposed are present.
之後，在真空室中使用反應性濺鍍法，乾蝕刻去除露出的a-Si膜。因此，殘存於a-Si膜上的光阻膜暴露於濺鍍中的電漿。在a-Si膜的蝕刻結束後，殘存的a-Si膜的圖案上的光阻膜使用樣品光阻剝離液剝離。 Thereafter, the exposed a-Si film was removed by dry etching using a reactive sputtering method in a vacuum chamber. Therefore, the photoresist film remaining on the a-Si film is exposed to the plasma in the sputtering. After the etching of the a-Si film is completed, the photoresist film on the pattern of the remaining a-Si film is peeled off using the sample photoresist stripper.
之後，洗淨基板，以光學顯微鏡一邊干涉一邊觀察a-Si膜上是否殘留光阻膜。被辨認出a-Si膜上光阻膜的殘留時，標記為「×」，未辨認出光阻膜的殘留時，標記為「○」。 Thereafter, the substrate was washed, and the photoresist was left on the a-Si film while interfering with the optical microscope. When the residue of the photoresist film on the a-Si film is recognized, it is marked as "x", and when the residue of the photoresist film is not recognized, it is marked as "○".
<基底的腐蝕程度> <degree of corrosion of the substrate>
製作基板上的銅膜和鋁膜，於上層製作形成絕緣材料的SiNx膜的層和不形成該膜的層。此為，閘線的圖案化、a-Si(n+)/a-Si膜的圖案化、SD線的圖案化、a-Si通道形成圖案化等。這些圖案化時使用光阻，為了剝離該光阻，使用光阻剝離液。最後，光阻剝離液為直接接觸銅膜和鋁膜的情形。此時，以SEM觀察光阻剝離液使銅膜和鋁膜腐蝕的程度。 A copper film and an aluminum film on the substrate were produced, and a layer of an SiNx film forming an insulating material and a layer not forming the film were formed on the upper layer. This is the patterning of the gate line, the patterning of the a-Si(n+)/a-Si film, the patterning of the SD line, and the patterning of the a-Si channel. A photoresist is used for these patterns, and a photoresist stripper is used in order to peel off the photoresist. Finally, the photoresist stripping solution is a case where the copper film and the aluminum film are directly contacted. At this time, the degree of corrosion of the copper film and the aluminum film by the photoresist stripping liquid was observed by SEM.
以下列三種作為基底膜準備。 The following three were prepared as the base film.
(1)在矽基板上形成100nm的矽熱氧化膜，以濺鍍法在熱氧化膜上形成300nm的銅膜者。表中記載為「Cu gate」。 (1) A 100 nm thermal oxide film was formed on a tantalum substrate, and a 300 nm copper film was formed on the thermal oxide film by sputtering. The table is described as "Cu gate".
(2)在矽基板上形成100nm的矽熱氧化膜，以濺鍍法在矽熱氧化膜上形成20nm的鉬膜後，再層積300nm的銅膜者。表中 記載為「Cu/Mo gate」。鉬為提高基板和銅膜接著力用的錨定層(anchor layer)。當銅膜成為此二層結構的情形，光阻剝離液使鉬層腐蝕，銅膜也變得無法使用。 (2) A 100 nm thermal oxide film was formed on the tantalum substrate, and a 20 nm molybdenum film was formed on the tantalum oxide film by sputtering, and then a 300 nm copper film was laminated. In the table It is described as "Cu/Mo gate". Molybdenum is an anchor layer for enhancing the adhesion of the substrate and the copper film. When the copper film becomes the two-layer structure, the photoresist stripping solution corrodes the molybdenum layer, and the copper film also becomes unusable.
(3)在矽基板上形成100nm的矽熱氧化膜，以濺鍍法在矽熱氧化膜上形成300nm的鋁膜者。表中記載為「Al gate」。 (3) A 100 nm thermal oxide film was formed on the tantalum substrate, and a 300 nm aluminum film was formed on the tantalum oxide film by sputtering. It is described as "Al gate" in the table.
這些膜在樣品光阻剝離液中浸漬10分鐘後，以SEM觀察膜。腐蝕的程度，假如為可作為製品使用的水準，標記為「○」，如為不能使用的水準，標記為「×」。 These films were immersed in the sample resist stripper for 10 minutes, and the film was observed by SEM. The degree of corrosion, if it is a level that can be used as a product, is marked as "○", and if it is an unusable level, it is marked as "X".
<樣品光阻剝離液> <sample photoresist stripping solution>
根據以下要領調製樣品光阻剝離液。樣品光阻剝離液以胺類、和極性溶劑、和水、和添加劑構成。 The sample resist stripper was prepared according to the following guidelines. The sample photoresist stripper is composed of an amine, a polar solvent, and water, and an additive.
(1)實施例1 (1) Embodiment 1
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 22.0質量% Propylene glycol (PG) 22.0% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑使用高哌嗪(homopiperazine)和山梨糖醇。 The additive used homopiperazine and sorbitol.
高哌嗪 1.0質量% High piperazine 1.0% by mass
山梨糖醇 1.0質量% Sorbitol 1.0% by mass
將上述混合攪拌，做成實施例1之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Example 1.
(2)實施例2 (2) Embodiment 2
實施例2較實施例1減少添加劑的量。 Example 2 reduces the amount of additive compared to Example 1.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 22.2質量% Propylene glycol (PG) 22.2% by mass
二乙二醇單丁基醚(BDG) 40質量% Diethylene glycol monobutyl ether (BDG) 40% by mass
水 31.0質量% Water 31.0% by mass
添加劑使用高哌嗪(homopiperazine)和山梨糖醇。 The additive used homopiperazine and sorbitol.
高哌嗪 0.9質量% High piperazine 0.9% by mass
山梨糖醇 0.9質量% Sorbitol 0.9% by mass
將上述混合攪拌，做成實施例2之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Example 2.
(3)實施例3 (3) Embodiment 3
實施例3較實施例2減少添加劑山梨糖醇的量。 Example 3 reduces the amount of additive sorbitol compared to Example 2.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 22.6質量% Propylene glycol (PG) 22.6 mass%
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑使用高哌嗪(homopiperazine)和山梨糖醇。 The additive used homopiperazine and sorbitol.
高哌嗪 0.9質量% High piperazine 0.9% by mass
山梨糖醇 0.5質量% Sorbitol 0.5% by mass
將上述混合攪拌，做成實施例3之樣品光阻剝離液。 The mixture was stirred and mixed to prepare a sample resist stripper of Example 3.
(4)實施例4 (4) Embodiment 4
實施例4對實施例1至3改變環胺的種類。 Example 4 changed the kind of cyclic amine for Examples 1 to 3.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 22.2質量% Propylene glycol (PG) 22.2% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑使用哌嗪(piperazine)和山梨糖醇。 The additive used piperazine and sorbitol.
哌嗪 0.9質量% Piperazine 0.9% by mass
山梨糖醇 0.9質量% Sorbitol 0.9% by mass
將上述混合攪拌，做成實施例4之樣品光阻剝離液。 The mixture was stirred and mixed to prepare a sample resist stripper of Example 4.
(5)實施例5 (5) Embodiment 5
實施例5對實施例1至4改變環胺的種類。 Example 5 changed the kind of cyclic amine for Examples 1 to 4.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 21.1質量% Propylene glycol (PG) 21.1% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑使用羥乙基哌嗪(OH-piperazine)和山梨糖醇。 The additive used hydroxy-ethyl piperazine (OH-piperazine) and sorbitol.
羥乙基哌嗪 2.0質量% Hydroxyethylpiperazine 2.0% by mass
山梨糖醇 0.9質量% Sorbitol 0.9% by mass
將上述混合攪拌，做成實施例5之樣品光阻剝離液。 The mixture was stirred and mixed to prepare a sample resist stripper of Example 5.
對於上述的實施例1至5的樣品光阻剝離液組成以及「光阻剝離性」和「基底的腐蝕程度」的結果，顯示於表1。 The results of the sample resist stripper composition and the "resistance peeling property" and the "corrosion degree of the substrate" of the above Examples 1 to 5 are shown in Table 1.
(6)比較例1 (6) Comparative Example 1
比較例1為沒有添加劑的組成。 Comparative Example 1 is a composition without an additive.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 24.0質量% Propylene glycol (PG) 24.0% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
將上述混合攪拌，做成比較例1之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 1.
(7)比較例2 (7) Comparative Example 2
比較例2改變胺的種類。 Comparative Example 2 changed the kind of amine.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N,N-二甲基乙醇胺(DMEA) 5.0質量% N,N-dimethylethanolamine (DMEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 24.0質量% Propylene glycol (PG) 24.0% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
將上述混合攪拌，做成比較例2之樣品光阻剝離液。 The mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 2.
(8)比較例3 (8) Comparative Example 3
比較例3改變胺的種類。 Comparative Example 3 changed the type of amine.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N,N-二乙基乙醇胺(N-DEEA) 5.0質量% N,N-diethylethanolamine (N-DEEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 24.0質量% Propylene glycol (PG) 24.0% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
將上述混合攪拌，做成比較例3之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 3.
(9)比較例4 (9) Comparative Example 4
比較例4改變胺的種類。 Comparative Example 4 changed the kind of amine.
使用二級烷醇胺為胺類。 The secondary alkanolamine is used as the amine.
N-甲基乙醇胺(MMA) 5.0質量% N-methylethanolamine (MMA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 24.0質量% Propylene glycol (PG) 24.0% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
將上述混合攪拌，做成比較例4之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 4.
(10)比較例5 (10) Comparative Example 5
比較例5改變胺的種類。 Comparative Example 5 changed the kind of amine.
使用一級烷醇胺為胺類。 The primary alkanolamine is used as the amine.
單乙醇胺(MEA) 5.0質量% Monoethanolamine (MEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 24.0質量% Propylene glycol (PG) 24.0% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
將上述混合攪拌，做成比較例5之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 5.
對於上述的比較例1至5的樣品光阻剝離液組成以及「光阻剝離性」和「基底的腐蝕程度」的結果，顯示於表2。 The results of the sample resist stripper composition and the "resistance peeling property" and the "corrosion degree of the substrate" of the above Comparative Examples 1 to 5 are shown in Table 2.
(11)比較例6 (11) Comparative Example 6
比較例6為比較例1添加添加劑。 Comparative Example 6 added an additive to Comparative Example 1.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 23.6質量% Propylene glycol (PG) 23.6 mass%
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
加入哌嗪(piperazine)作為添加劑。 Piperazine was added as an additive.
哌嗪 0.4質量% Piperazine 0.4% by mass
將上述混合攪拌，做成比較例6之樣品光阻剝離液。 The mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 6.
(12)比較例7 (12) Comparative Example 7
比較例7為增加比較例6的添加劑的量。 Comparative Example 7 is to increase the amount of the additive of Comparative Example 6.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 23.1質量% Propylene glycol (PG) 23.1% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
加入哌嗪(piperazine)作為添加劑。 Piperazine was added as an additive.
哌嗪 0.9質量% Piperazine 0.9% by mass
將上述混合攪拌，做成比較例7之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 7.
(13)比較例8 (13) Comparative Example 8
比較例8為改變比較例6的添加劑種類，量也增加。 In Comparative Example 8, the type of the additive of Comparative Example 6 was changed, and the amount was also increased.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 23.0質量% Propylene glycol (PG) 23.0% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
加入羥乙基哌嗪(OH-piperazine)作為添加劑。 Hydroxyethylpiperazine (OH-piperazine) was added as an additive.
羥乙基哌嗪 1.0質量% Hydroxyethylpiperazine 1.0% by mass
將上述混合攪拌，做成比較例8之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 8.
(14)比較例9 (14) Comparative Example 9
比較例9為增加比較例8的添加劑的量。 Comparative Example 9 is an increase in the amount of the additive of Comparative Example 8.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 21.6質量% Propylene glycol (PG) 21.6 mass%
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
加入羥乙基哌嗪(OH-piperazine)作為添加劑。 Hydroxyethylpiperazine (OH-piperazine) was added as an additive.
羥乙基哌嗪 2.4質量% Hydroxyethylpiperazine 2.4% by mass
將上述混合攪拌，做成比較例9之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 9.
(15)比較例10 (15) Comparative Example 10
比較例10為改變比較例6的添加劑種類，量也增加。 In Comparative Example 10, the kind of the additive of Comparative Example 6 was changed, and the amount was also increased.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 23.0質量% Propylene glycol (PG) 23.0% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
加入高哌嗪(homopiperazine)作為添加劑。 Homopiperazine was added as an additive.
高哌嗪 1.0質量% High piperazine 1.0% by mass
將上述混合攪拌，做成比較例10之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 10.
(16)比較例11 (16) Comparative Example 11
比較例11為減少比較例10的添加劑的量。 Comparative Example 11 is to reduce the amount of the additive of Comparative Example 10.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 23.1質量% Propylene glycol (PG) 23.1% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
加入高哌嗪(homopiperazine)作為添加劑。 Homopiperazine was added as an additive.
高哌嗪 0.9質量% High piperazine 0.9% by mass
將上述混合攪拌，做成比較例11之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 11.
(17)比較例12 (17) Comparative Example 12
比較例12為減少比較例11的添加劑的量。 Comparative Example 12 is to reduce the amount of the additive of Comparative Example 11.
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 23.3質量% Propylene glycol (PG) 23.3 mass%
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
加入高哌嗪(homopiperazine)作為添加劑。 Homopiperazine was added as an additive.
高哌嗪 0.7質量% High piperazine 0.7% by mass
將上述混合攪拌，做成比較例12之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 12.
對於上述的比較例6至12的樣品光阻剝離液組成以及「光阻剝離性」和「基底的腐蝕程度」的結果，顯示於表3。 The results of the sample resist stripper composition and the "resistance peeling property" and the "corrosion degree of the substrate" of the above Comparative Examples 6 to 12 are shown in Table 3.
參照表1，首先實施例1至5的各樣品光阻剝離液，當然可剝離濕蝕刻後的光阻膜，對於考量乾蝕刻時暴露於電漿而變質的a-Si膜上的乾蝕刻後的光阻膜，也可充分地剝離。 Referring to Table 1, first of each of the sample resist stripping solutions of Examples 1 to 5, of course, the wet-etched photoresist film can be peeled off, after dry etching on the a-Si film which is deteriorated by exposure to plasma during dry etching. The photoresist film can also be sufficiently peeled off.
另一方面，對於基底的腐蝕，不論是銅膜、鉬膜上的銅膜、鋁膜任一種膜，以10分鐘的浸漬，都為充分作為製品而可使用的程度的腐蝕。亦即，實施例1至5的各樣品光阻剝離液，在濕蝕刻、乾蝕刻沒有區別，可使光阻膜剝離，且基底即使是銅膜、即使是鉬膜上的銅膜、即使是鋁膜，皆為非常低的腐蝕程度。 On the other hand, the corrosion of the substrate, whether it is a copper film, a copper film on a molybdenum film, or an aluminum film, is impregnated for 10 minutes, and is corrosion to a sufficient extent as a product. That is, in each of the sample resist stripping liquids of Examples 1 to 5, there is no difference between wet etching and dry etching, and the photoresist film can be peeled off, and even the substrate is a copper film, even a copper film on the molybdenum film, even if Aluminum films are all very low corrosion levels.
因此，實施例1至5的各樣品光阻剝離液為一個光阻剝離液，基底即使為鋁膜、即使為銅膜、即使為鉬膜上的銅膜，皆可使用。此處，實施例1至5皆為環胺(哌嗪、羥乙基哌嗪、高哌嗪)和糖醇(山梨糖醇)的組合。 Therefore, each of the sample resist stripping liquids of Examples 1 to 5 is a resist stripping liquid, and even if the substrate is an aluminum film, even a copper film or a copper film on a molybdenum film can be used. Here, Examples 1 to 5 are each a combination of a cyclic amine (piperazine, hydroxyethylpiperazine, homopiperazine) and a sugar alcohol (sorbitol).
繼續參照表2。比較例1至3為使用三級烷醇胺、完全不含添加劑的樣品光阻剝離液。此種組成雖然基底的腐蝕低，但是對於乾蝕刻後的光阻膜則無法剝離。 Continue to refer to Table 2. Comparative Examples 1 to 3 are sample resist strippers using a tertiary alkanolamine and completely free of additives. Although the composition has low corrosion of the substrate, the photoresist film after dry etching cannot be peeled off.
比較例4、5為胺級數變小，使用二級烷醇胺、一級烷醇胺者。此種組成，可使乾蝕刻後的光阻膜剝離。但是，銅膜及鉬膜上的銅膜受到作為製品而無法使用的程度的腐蝕。因此，級數小的胺雖然剝離光阻膜的作用強，同時也腐蝕基底(特別是銅膜)。判斷這是因為胺和銅膜之間形成錯合物的緣故。又鋁膜不易形成錯合物，即使級數小的胺也不會被腐蝕。 In Comparative Examples 4 and 5, the number of amines was small, and those using a secondary alkanolamine or a primary alkanolamine were used. With such a composition, the photoresist film after dry etching can be peeled off. However, the copper film on the copper film and the molybdenum film is corroded to such an extent that it cannot be used as a product. Therefore, the amine having a small number of stages has a strong effect of peeling off the photoresist film and also corrodes the substrate (especially a copper film). This was judged to be due to the formation of a complex between the amine and the copper film. Further, the aluminum film is less likely to form a complex compound, and even an amine having a small number of stages is not corroded.
繼續參照表3。比較例6至12係為了低抑制基底的腐蝕，確保乾蝕刻後的光阻膜的剝離性，而探討添加劑者。哌 嗪為環胺，雖然是作為添加劑，但對光阻膜可期待與添加級數低的胺有相同的效果。又因為具有所謂環式的立體結構，也可期待抑制被考量在銅和胺之間所形成的錯合物的形成的效果。 Continue to refer to Table 3. In Comparative Examples 6 to 12, in order to suppress corrosion of the substrate with low suppression, and to ensure the peeling property of the photoresist film after dry etching, the additive was examined. Piper Although the azine is a cyclic amine, it is an additive, but it is expected that the photoresist film has the same effect as an amine having a low number of addition stages. Further, since it has a so-called ring-shaped three-dimensional structure, it is expected to suppress the effect of considering the formation of a complex formed between copper and an amine.
從僅使用哌嗪作為添加劑的比較例6和7來看，視哌嗪的含量，可剝離乾蝕刻後的光阻膜，相反地也會腐蝕基底。 From the comparison of Comparative Examples 6 and 7 using only piperazine as an additive, the content of the piperazine was peeled off from the dry-etched photoresist film, and conversely, the substrate was also etched.
比較例8和9為僅使用羥乙基哌嗪作為添加劑的結果。由於增加添加量，羥乙基哌嗪也可使乾蝕刻後的光阻膜剝離，但是同時也會腐蝕基底。 Comparative Examples 8 and 9 are the results of using only hydroxyethylpiperazine as an additive. Hydroxyethylpiperazine also allows the dry-etched photoresist film to be peeled off by increasing the amount of addition, but also corrodes the substrate.
比較例10至12為僅使用高哌嗪作為添加劑的情形。高哌嗪為約0.9質量%至1.0質量%，可使乾蝕刻後的光阻膜剝離。但是基底為鋁膜的情形被認為會腐蝕基底。 Comparative Examples 10 to 12 are cases in which only high piperazine was used as an additive. The homopiperazine is from about 0.9% by mass to 1.0% by mass, and the photoresist film after dry etching can be peeled off. However, the case where the substrate is an aluminum film is considered to corrode the substrate.
根據上述，由於環胺含有約數個質量%，可使得難以剝離的乾蝕刻後的光阻膜剝離。但是，伴隨地，也會腐蝕銅膜及鋁膜。然而，由於同時添加約數個質量%的糖醇，可使光阻膜的剝離性、和銅膜(包括鉬膜/銅膜)及鋁膜兩者的抑制腐蝕都能達到。 According to the above, since the cyclic amine contains about several mass%, the dry-etched photoresist film which is difficult to peel off can be peeled off. However, concomitantly, the copper film and the aluminum film are also corroded. However, since about several mass% of the sugar alcohol is simultaneously added, the peeling property of the photoresist film, and the corrosion inhibition of both the copper film (including the molybdenum film/copper film) and the aluminum film can be achieved.
如上所述，本發明所述的光阻剝離液由於同時存在環胺和糖醇，基底即使是銅膜、即使是鋁膜，更不用說光阻膜，即使是在乾蝕刻步驟暴露於電漿而變質的光阻膜，可以低抑制基底的腐蝕而同時剝離。 As described above, since the photoresist stripping liquid of the present invention has both a cyclic amine and a sugar alcohol, the substrate is even a copper film, even an aluminum film, not to mention a photoresist film, even when exposed to a plasma in a dry etching step. The deteriorated photoresist film can suppress the corrosion of the substrate at the same time and peel off at the same time.
以下對於使用二級烷醇胺作為添加劑的情形，以實施例和比較例說明之。 Hereinafter, the case of using a secondary alkanolamine as an additive will be described by way of examples and comparative examples.
(18)實施例21 (18) Example 21
使用三級烷醇胺為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 21.7質量% Propylene glycol (PG) 21.7 mass%
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑使用N-甲基乙醇胺(MMA)和山梨糖醇。 The additive used N-methylethanolamine (MMA) and sorbitol.
MMA 1.4質量% MMA 1.4% by mass
山梨糖醇 0.9質量% Sorbitol 0.9% by mass
將上述混合攪拌，做成實施例21之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Example 21.
(19)比較例21 (19) Comparative Example 21
比較例21為減少實施例21的MMA的量。 Comparative Example 21 is to reduce the amount of MMA of Example 21.
使用三級烷醇胺作為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 22.2質量% Propylene glycol (PG) 22.2% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑使用N-甲基乙醇胺(MMA)和山梨糖醇。 The additive used N-methylethanolamine (MMA) and sorbitol.
MMA 0.9質量% MMA 0.9% by mass
山梨糖醇 0.9質量% Sorbitol 0.9% by mass
將上述混合攪拌，做成比較例21之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 21.
(20)比較例22 (20) Comparative Example 22
比較例22為增加比較例21的MMA的量。 Comparative Example 22 is an increase in the amount of MMA of Comparative Example 21.
使用三級烷醇胺作為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 21.9質量% Propylene glycol (PG) 21.9% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑使用N-甲基乙醇胺(MMA)和山梨糖醇。 The additive used N-methylethanolamine (MMA) and sorbitol.
MMA 1.2質量% MMA 1.2% by mass
山梨糖醇 0.9質量% Sorbitol 0.9% by mass
將上述混合攪拌，做成比較例22之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 22.
(21)比較例23 (21) Comparative Example 23
比較例23為增加比較例22的MMA的量。 Comparative Example 23 is to increase the amount of MMA of Comparative Example 22.
使用三級烷醇胺作為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 21.8質量% Propylene glycol (PG) 21.8 mass%
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑使用N-甲基乙醇胺(MMA)和山梨糖醇。 The additive used N-methylethanolamine (MMA) and sorbitol.
MMA 1.3質量% MMA 1.3% by mass
山梨糖醇 0.9質量% Sorbitol 0.9% by mass
將上述混合攪拌，做成比較例23之樣品光阻剝離液。 The mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 23.
對於上述的實施例21及比較例21至23的樣品光阻剝離液組成以及「光阻剝離性」和「基底的腐蝕程度」的結果，顯示於表4。 The results of the sample resist stripper composition and the "resistance peeling property" and the "corrosion degree of the substrate" of the above-described Example 21 and Comparative Examples 21 to 23 are shown in Table 4.
(22)比較例24 (22) Comparative Example 24
比較例24為實施例21中刪除山梨糖醇。 Comparative Example 24 is the removal of sorbitol in Example 21.
使用三級烷醇胺作為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 22.6質量% Propylene glycol (PG) 22.6 mass%
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑僅使用N-甲基乙醇胺(MMA)。 The additive used only N-methylethanolamine (MMA).
MMA 1.4質量% MMA 1.4% by mass
將上述混合攪拌，做成比較例24之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 24.
(23)比較例25 (23) Comparative Example 25
比較例25為比較例24的添加劑改變為N-乙基乙醇胺(MEM)且量也增加。 In Comparative Example 25, the additive of Comparative Example 24 was changed to N-ethylethanolamine (MEM) and the amount was also increased.
使用三級烷醇胺作為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 22.4質量% Propylene glycol (PG) 22.4% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑只使用N-乙基乙醇胺(MEM)。 The additive used only N-ethylethanolamine (MEM).
MEM 1.6質量% MEM 1.6% by mass
將上述混合攪拌，做成比較例25之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 25.
(24)比較例26 (24) Comparative Example 26
比較例26為比較例24的添加劑改變為N-正丁基乙醇胺(MBM)且量也增加。 In Comparative Example 26, the additive of Comparative Example 24 was changed to N-n-butylethanolamine (MBM) and the amount was also increased.
使用三級烷醇胺作為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 21.9質量% Propylene glycol (PG) 21.9% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑只使用N-正丁基乙醇胺(MBM)。 The additive used only N-n-butylethanolamine (MBM).
MBM 2.1質量% MBM 2.1% by mass
將上述混合攪拌，做成比較例26之樣品光阻剝離液。 The above mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 26.
(25)比較例27 (25) Comparative Example 27
比較例27為比較例24的添加劑改變為二乙醇胺(DEA)且量也增加。 In Comparative Example 27, the additive of Comparative Example 24 was changed to diethanolamine (DEA) and the amount was also increased.
使用三級烷醇胺作為胺類。 A tertiary alkanolamine is used as the amine.
N-甲基二乙醇胺(MDEA) 5.0質量% N-methyldiethanolamine (MDEA) 5.0% by mass
極性溶劑混合兩種。 Two kinds of polar solvents are mixed.
丙二醇(PG) 22.1質量% Propylene glycol (PG) 22.1% by mass
二乙二醇單丁基醚(BDG) 40.0質量% Diethylene glycol monobutyl ether (BDG) 40.0% by mass
水 31.0質量% Water 31.0% by mass
添加劑只使用二乙醇胺(DEA)。 The additive uses only diethanolamine (DEA).
DEA 1.9質量% DEA 1.9 mass%
將上述混合攪拌，做成比較例27之樣品光阻剝離液。 The mixture was stirred and mixed to prepare a sample resist stripper of Comparative Example 27.
對於上述比較例24至27的樣品光阻剝離液組成以 及「光阻剝離性」和「基底的腐蝕程度」的結果，顯示於表5。 For the sample resist stripping liquid compositions of Comparative Examples 24 to 27 above, The results of "resistance peeling" and "corrosion of substrate" are shown in Table 5.
參照表4，關於本發明的實施例21的樣品光阻剝離液當然可剝離濕蝕刻後的光阻膜，對於考量乾蝕刻時暴露於電漿而變質的a-Si膜上的乾蝕刻後的光阻膜，也可充分地剝離。 Referring to Table 4, the sample resist stripping liquid of Example 21 of the present invention can of course be peeled off from the wet-etched photoresist film for dry etching after considering the deterioration of the a-Si film which is exposed to the plasma during dry etching. The photoresist film can also be sufficiently peeled off.
又參照實施例21及比較例21至23，作為添加劑使用的二級烷醇胺MMA，由於含量為1.3質量%以下，無法使乾蝕刻後的光阻膜剝離。因此可知，必須在相對於光阻剝離液全量為1.4質量%以上。對此，如比較例4所示，MMA相對於光阻剝離液全量含有5.0質量%時，會使銅膜腐蝕。因此，MMA的含量上限為，相對於光阻剝離液全量，未滿5.0質量%。 Further, referring to Example 21 and Comparative Examples 21 to 23, the secondary alkanolamine MMA used as an additive had a content of 1.3% by mass or less, and the photoresist film after dry etching could not be peeled off. Therefore, it is understood that it is necessary to be 1.4% by mass or more based on the total amount of the resist stripping liquid. On the other hand, as shown in Comparative Example 4, when the MMA was contained in an amount of 5.0% by mass based on the total amount of the resist release liquid, the copper film was corroded. Therefore, the upper limit of the content of MMA is less than 5.0% by mass based on the total amount of the resist stripper.
表5中顯示添加劑中不含山梨糖醇的組成之結果。不含山梨糖醇，即使是作為添加劑使用的情形，二級烷醇胺會腐蝕銅膜(參照比較例24)。另一方面，即使是二級烷醇胺，MEM、MBM、DEA雖然為添加劑而含有，也無法去除乾蝕刻後的光阻膜。 Table 5 shows the results of the composition containing no sorbitol in the additive. Without sorbitol, the secondary alkanolamine corrodes the copper film even when used as an additive (refer to Comparative Example 24). On the other hand, even if it is a secondary alkanolamine, although MEM, MBM, and DEA are contained as an additive, the photoresist film after dry etching cannot be removed.
因此，直鏈的二級胺也可以達到本發明目的之不腐蝕銅膜等、且可使變質的光阻膜剝離的效果者，限於部分的二級胺。 Therefore, the linear secondary amine can also achieve the effect of not corroding the copper film or the like and peeling off the deteriorated photoresist film for the purpose of the present invention, and is limited to a part of the secondary amine.
如上所述，作為添加劑的二級烷醇胺之N-甲基乙醇胺(MMA)，由於與糖醇同時存在，基底即使是銅膜、即使是鋁膜，更不用說光阻膜，即使是在乾蝕刻步驟暴露於電漿而變質的光阻膜，也可低抑制基底的腐蝕而同時剝離。 As described above, the N-methylethanolamine (MMA) of the secondary alkanolamine as an additive, even if it is a copper film, even an aluminum film, not to mention a photoresist film, even if it is present at the same time as the sugar alcohol The photoresist film which is exposed to the plasma by the dry etching step may also suppress the corrosion of the substrate while peeling off at the same time.
本發明的光阻剝離液可作為使用正型光阻的情形之光阻剝離液而適宜利用。其可一般適用於液晶顯示器、電漿 顯示器、有機電致發光等的平面顯示器(FPD)的製造。 The photoresist stripping liquid of the present invention can be suitably used as a photoresist stripping liquid in the case of using a positive photoresist. It can be generally applied to liquid crystal displays, plasma Manufacture of flat panel displays (FPDs) such as displays, organic electroluminescence, and the like.
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| KR20100070087A (en) * | 2008-12-17 | 2010-06-25 | 삼성전자주식회사 | Composition for photoresist stripper and method of fabricating thin film transistor array substrate |
| JP5288144B2 (en) * | 2008-12-25 | 2013-09-11 | ナガセケムテックス株式会社 | Photoresist stripper composition, photoresist stripping method and manufacturing method for laminated metal wiring board |
| KR101668126B1 (en) * | 2009-04-17 | 2016-10-20 | 나가세케무텍쿠스가부시키가이샤 | Photoresist remover composition and method for removing photoresist |
| KR100950779B1 (en) * | 2009-08-25 | 2010-04-02 | 엘티씨 (주) | Composition of stripper for all tft-lcd process photoresist |
| JP5717519B2 (en) * | 2011-04-15 | 2015-05-13 | パナソニック株式会社 | Stripper for photoresist |
| KR20140030185A (en) * | 2011-05-20 | 2014-03-11 | 파나소닉 주식회사 | Photoresist stripping solution, stripping solution recycling system and operating method, and method for recycling stripping solution |
| CN103064263B (en) * | 2011-08-22 | 2015-06-10 | 东友精细化工有限公司 | Resist stripper composition and method of stripping resist using same |
-
2013
- 2013-09-13 JP JP2013190455A patent/JP5575318B1/en not_active Expired - Fee Related
-
2014
- 2014-02-17 CN CN201610810602.2A patent/CN106200283B/en active Active
- 2014-02-17 CN CN201480059453.XA patent/CN105723284B/en active Active
- 2014-02-17 WO PCT/JP2014/000786 patent/WO2015029277A1/en active Application Filing
- 2014-05-29 JP JP2014111594A patent/JP5593466B1/en active Active
- 2014-07-09 TW TW103123581A patent/TWI494712B/en active
- 2014-07-09 TW TW103128915A patent/TWI494713B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI705157B (en) * | 2017-02-10 | 2020-09-21 | 日商荒川化學工業股份有限公司 | Remover for anti-rust film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5593466B1 (en) | 2014-09-24 |
| CN105723284A (en) | 2016-06-29 |
| TWI494713B (en) | 2015-08-01 |
| CN106200283B (en) | 2017-11-03 |
| TW201447513A (en) | 2014-12-16 |
| JP5575318B1 (en) | 2014-08-20 |
| WO2015029277A1 (en) | 2015-03-05 |
| TWI494712B (en) | 2015-08-01 |
| JP2015064555A (en) | 2015-04-09 |
| CN106200283A (en) | 2016-12-07 |
| CN105723284B (en) | 2017-10-03 |
| JP2015064393A (en) | 2015-04-09 |
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