TW201432395A - Composition for photoresist stripping solution and stripping method of photoresist using the same - Google Patents
Composition for photoresist stripping solution and stripping method of photoresist using the same Download PDFInfo
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—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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- 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
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
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Abstract
Description
本發明有關一種光阻剝離液組成物，以及一種光阻剝離方法，更具體而言，係有關一種可降低金屬佈線腐蝕，同時既環保又對人體與環境無害但能展現出優異剝離性能的光阻剝離液組成物，以及使用該組成物的光阻剝離方法。 The invention relates to a photoresist stripping liquid composition, and a photoresist stripping method, and more particularly to a light which can reduce the corrosion of metal wiring and is environmentally friendly and harmless to the human body and the environment but exhibits excellent peeling performance. A resist stripping composition, and a photoresist stripping method using the composition.
光阻(photo-resist)是光罩蝕刻製程(photolithography process)中不可缺少的物質，而光罩蝕刻製程是一般用於製造諸如積體電路(Integrated circuit,IC)、大型積體電路(large scale integration,LSI)、超大型積體電路(very large scale integration,VLSI)等等半導體裝置，以及諸如電漿顯示裝置(plasma display device,PDP)等等圖像顯示裝置常用的製程之一。 Photo-resist is an indispensable substance in the photolithography process, and the photomask etching process is generally used for manufacturing such as integrated circuits (ICs) and large scale circuits. One of the processes commonly used for semiconductor devices such as integration, LSI), very large scale integration (VLSI), and image display devices such as plasma display devices (PDPs).
光罩蝕刻製程結束之後，光阻在高溫下被剝離溶液去除，但在去除光阻的過程中，位於底部的金屬薄膜層可能會被剝離溶液腐蝕。因此，需要一種能展現出優異的光阻去除效果，但又能將金屬薄膜層的腐蝕降至最低的方法。 After the photomask etching process is finished, the photoresist is removed by the stripping solution at a high temperature, but during the process of removing the photoresist, the metal film layer at the bottom may be corroded by the stripping solution. Therefore, there is a need for a method which exhibits excellent photoresist removal effects while minimizing corrosion of the metal film layer.
同時，隨著圖案微型化的趨勢，金屬以及氧化膜的蝕刻 條件變得非常嚴苛，以致增加對光阻的破壞以及造成光阻劑變化。由於這個原因，縱使已使用有機溶劑處理，光阻劑仍然會殘留在基板上，因此，需要一種剝離性能強但不會殘留的剝離液組成物。 At the same time, as the pattern is miniaturized, metal and oxide film etching The conditions become so severe that the damage to the photoresist is increased and the photoresist is changed. For this reason, even if it has been treated with an organic solvent, the photoresist remains on the substrate, and therefore, a peeling liquid composition which is strong in peeling property but does not remain is required.
習知光阻剝離液組成物係以胺類化合物、有機溶劑為基礎，或者額外使用防腐劑以移除光阻。 Conventional photoresist stripper compositions are based on amine compounds, organic solvents, or additional preservatives to remove photoresist.
習知光阻剝離液組成物包含諸如單乙醇胺等等的有機胺類化合物；諸如N-甲基吡咯烷酮(NMP)、二甲基亞碸(DMSO)等等的非質子溶劑；及/或諸如乙二醇醚類的質子溶劑。然而，用於習知光阻剝離液組成物中的乙二醇醚類質子溶劑具有很強的毒性，會造成大腦與神經受損，而導致昏迷以及諸如頭痛、異位性皮膚炎、過敏性鼻炎、氣喘等等的環境疾病。因此，需要開發出一種能夠替代乙二醇醚且能夠實現與使用乙二醇醚之習知光阻剝離液組成物相同或是更優異的剝離效果的溶劑。 The conventional photoresist stripper composition comprises an organic amine compound such as monoethanolamine or the like; an aprotic solvent such as N-methylpyrrolidone (NMP), dimethylhydrazine (DMSO), and the like; and/or such as ethylene glycol. Proton solvent for ethers. However, the glycol ether protic solvent used in the conventional photoresist stripper composition is highly toxic, causing damage to the brain and nerves, leading to coma and such as headache, atopic dermatitis, allergic rhinitis, Environmental diseases such as asthma. Therefore, there is a need to develop a solvent which can replace the glycol ether and which can achieve the same or superior peeling effect as the conventional photoresist stripper composition using glycol ether.
本發明之一目的在於提供一種光阻剝離液組成物，其可降低金屬佈線的腐蝕，同時既環保又對人體與環境無害，但能展現出優異的剝離性能。 An object of the present invention is to provide a photoresist stripping liquid composition which can reduce corrosion of a metal wiring while being environmentally friendly and harmless to the human body and the environment, but exhibits excellent peeling performance.
本發明之另一目的在於提供一種環保的光阻剝離方法，其可展現出優異的剝離性能。 Another object of the present invention is to provide an environmentally friendly photoresist peeling method which exhibits excellent peeling properties.
本發明提供一種光阻剝離液組成物，包含：10至90重量 百分比(wt%)的N,N-二甲基丙醯胺(N,N-dimethyl propionamide)、5至80重量百分比(wt%)的丙酮縮甘油(Solketal)、以及1至20重量百分比(wt%)的有機胺類化合物(organic amine)。 The invention provides a photoresist stripping liquid composition comprising: 10 to 90 weight Percent (wt%) of N,N-dimethyl propionamide, 5 to 80 weight percent (wt%) of acetal glycerol (Solketal), and 1 to 20 weight percent (wt %) of an organic amine.
本發明也提供一種使用該光阻剝離液組成物的光阻剝離方法。 The present invention also provides a photoresist stripping method using the photoresist stripper composition.
以下將進一步詳細說明依據本發明之特定實施例的光阻剝離液組成物以及光阻剝離方法。 The photoresist stripper composition and the photoresist stripping method according to a specific embodiment of the present invention will be described in further detail below.
依據本發明一實施例，一光阻剝離液組成物包含有10至90重量百分比(wt%)的N,N-二甲基丙醯胺、5至80重量百分比(wt%)的丙酮縮甘油、以及1至20重量百分比(wt%)的有機胺類化合物。 According to an embodiment of the invention, a photoresist stripper composition comprises 10 to 90 weight percent (wt%) of N,N-dimethylpropionamide, and 5 to 80 weight percent (wt%) of acetone glycerol And 1 to 20 weight percent (wt%) of an organic amine compound.
較佳為，該光阻剝離液組成物可包含有15至75重量百分比(wt%)的N,N-二甲基丙醯胺、10至70重量百分比(wt%)的丙酮縮甘油、以及1至15重量百分比(wt%)的有機胺類化合物。 Preferably, the photoresist stripper composition may comprise 15 to 75 weight percent (wt%) of N,N-dimethylpropionamide, 10 to 70 weight percent (wt%) of acetone glycerol, and 1 to 15 weight percent (wt%) of an organic amine compound.
本發明之發明人察覺到在習知光阻剝離液組成物中執行各種功能之乙二醇醚溶劑對於環境以及人體方面的問題，遂逐步研究能夠替代前述乙二醇醚溶劑的物質，並透過諸多實驗證實包含有丙酮縮甘油((2,2-二甲基-1,3-二氧戊環-4-基)甲醇((2,2-dimethyl-1,3-dioxolan-4-yl)methanol))的光阻剝離液組成物可降低金屬佈線的腐蝕，同時對人體以及環境無害，但卻能夠展現出與習知光阻剝離液組成物相同或更優異的剝離性能，因而完成本發明。 The inventors of the present invention perceive the environmental and human problems of glycol ether solvents which perform various functions in the conventional photoresist stripping liquid composition, and gradually study substances which can replace the aforementioned glycol ether solvent, and pass through many experiments. It was confirmed to contain (2,2-dimethyl-1,3-dioxolan-4-yl)methanol ((2,2-dimethyl-1,3-dioxolan-4-yl)methanol) The photoresist stripper composition can reduce the corrosion of the metal wiring while being harmless to the human body and the environment, but can exhibit the same or superior peeling performance as the conventional photoresist stripper composition, and thus the present invention has been completed.
該光阻剝離液組成物使用丙酮縮甘油((2,2-二甲基-1,3-二氧戊環-4-基)甲醇)作為特定溶劑，其可替代先前使用的乙二醇醚質 子溶劑。 The photoresist stripper composition uses acetone glycerol ((2,2-dimethyl-1,3-dioxolan-4-yl)methanol) as a specific solvent, which can replace the previously used glycol ether quality Sub-solvent.
雖然先前使用的乙二醇醚質子溶劑可減少於高溫下移除光阻過程中的溶劑揮發，且可降低光阻與底部金屬薄膜層之間的表面張力，來提高光阻去除效率，然而，乙二醇醚溶劑可能會容易揮發並透過呼吸作用而容易被人體吸收，乙二醇醚溶劑多數都具有很強的毒性且會造成大腦與神經受損，而導致昏迷以及諸如頭痛、異位性皮膚炎、過敏性鼻炎、氣喘等等的環境疾病。 Although the previously used glycol ether proton solvent can reduce the solvent volatilization during the removal of the photoresist at a high temperature, and can reduce the surface tension between the photoresist and the bottom metal film layer, thereby improving the photoresist removal efficiency, however, Glycol ether solvents may be easily volatilized and easily absorbed by the body through respiration. Most of the glycol ether solvents are highly toxic and cause damage to the brain and nerves, leading to coma and headaches, ectopicities. Environmental diseases such as dermatitis, allergic rhinitis, and asthma.
相反的，丙酮縮甘油具有包括兩個烷基的化學結構，同時，其可容易並有效地去除光阻但卻不會產生有害性的副產物或環境污染物。因此，由於本發明之含有丙酮縮甘油的光阻剝離液組成物不含對環境以及人體有害的乙二醇醚，因此極為環保，且能夠展現出改善的光阻剝離效果，同時能夠降低金屬佈線的腐蝕。 In contrast, acetone glycerol has a chemical structure including two alkyl groups, and at the same time, it can easily and efficiently remove photoresist without causing harmful by-products or environmental pollutants. Therefore, since the composition of the acetal glycerin-containing photoresist stripping liquid of the present invention does not contain a glycol ether which is harmful to the environment and the human body, it is extremely environmentally friendly and can exhibit an improved photoresist peeling effect while reducing metal wiring. Corrosion.
以該光阻剝離液組成物的總量為基準，丙酮縮甘油的使用量最好為5至80重量百分比(wt%)，較佳為10至70重量百分比(wt%)。若丙酮縮甘油的使用量低於5重量百分比(wt%)，溶劑的含量會過低導致難以清洗；若丙酮縮甘油的使用量高於80重量百分比(wt%)，光阻的剝離性能可能會降低。 The acetone glycerin is preferably used in an amount of 5 to 80% by weight (wt%), preferably 10 to 70% by weight (% by weight) based on the total mass of the resist stripper composition. If the amount of acetone glycerin used is less than 5 weight percent (wt%), the solvent content may be too low to cause difficulty in cleaning; if the amount of acetone glycerol used is more than 80 weight percent (wt%), the peeling performance of the photoresist may be Will decrease.
前述有機胺類化合物同時包括脂肪族有機胺以及環狀有機胺。前述有機胺類化合物是強鹼物質，其極容易滲透到在諸如乾式或濕式蝕刻、灰化(ashing)、或是離子植入(ion implantation)等等各種製程條件下變質或是交聯光阻的高分子基質中，而破壞分子內或是分子之間的吸引力。由於胺類化合物的作用，殘留於基板上之光阻中結 構脆弱的部分會形成空間，而將光阻改變為非結晶高分子凝膠塊(amorphous polymer gel mass)，從而能夠容易地去除附著在基板上的光阻。 The aforementioned organic amine compound includes both an aliphatic organic amine and a cyclic organic amine. The aforementioned organic amine compound is a strong base substance which is extremely easy to penetrate into various processes such as dry or wet etching, ashing, or ion implantation, or to crosslink light. Blocking in the polymer matrix, destroying the attraction within or between molecules. Due to the action of the amine compound, the photoresist remaining in the substrate is blocked The fragile portion forms a space, and the photoresist is changed to an amorphous polymer gel mass, so that the photoresist attached to the substrate can be easily removed.
以該光阻剝離液組成物的總量為基準，前述有機胺類化合物的含量最好為1至20重量百分比(wt%)，較佳為1至15重量百分比(wt%)。以該光阻剝離液組成物的總量為基準，若前述有機胺類化合物的含量低於1重量百分比(wt%)，光阻的剝離性能可能會降低；若前述有機胺類化合物的含量高於20重量百分比(wt%)，降低金屬腐蝕的性能可能會減弱，且揮發速度可能會加速，而不利於使用。 The content of the above organic amine compound is preferably from 1 to 20% by weight (wt%), preferably from 1 to 15% by weight (% by weight) based on the total mass of the resist stripper composition. Based on the total amount of the resist stripper composition, if the content of the organic amine compound is less than 1% by weight (wt%), the peeling performance of the photoresist may be lowered; if the content of the organic amine compound is high At 20 weight percent (wt%), the performance of reducing metal corrosion may be weakened, and the volatilization rate may be accelerated, which is unfavorable for use.
關於前述有機胺類化合物，可以使用一級、二級或三級脂肪胺。前述一級脂肪胺可包括單乙醇胺(monoethanolamine,MEA)、乙二胺(ethylenediamine)、2-(2-胺基乙氧基)乙醇(2-(2-aminoethoxy)ethanol)、2-(2-胺基乙胺基)乙醇(2-(2-aminoethylamino)ethanol)、1-胺基-2-丙醇(1-amino-2-propanol)等等；前述二級脂肪胺可包括二乙醇胺(diethanolamine)、亞胺二丙胺(iminobispropylamine)、2-甲胺乙醇(2-methylamino ethanol)(N-甲基乙醇胺(N-methylethanolamine))等等；前述三級脂肪胺可包括甲基二乙醇胺(methyldiethanolamine)、三乙胺基乙醇(triethylaminoethanol)等等。 As the aforementioned organic amine compound, a primary, secondary or tertiary aliphatic amine can be used. The aforementioned primary aliphatic amine may include monoethanolamine (MEA), ethylenediamine, 2-(2-aminoethoxy)ethanol, 2-(2-amine) 2-(2-aminoethylamino)ethanol, 1-amino-2-propanol, etc.; the aforementioned secondary fatty amine may include diethanolamine , iminobispropylamine, 2-methylaminoethanol (N-methylethanolamine), etc.; the aforementioned tertiary aliphatic amine may include methyldiethanolamine, Triethylaminoethanol and the like.
並且，前述環狀有機胺可包括1-(2-羥乙基)哌嗪(1-(2-hydroxyethyl)piperazine,HEP)、1-(2-胺乙基)哌嗪(1-(2-aminoethyl)piperazine)、1-(2-羥乙基)甲基哌嗪(1-(2-hydroxyethyl)methylpiperazine)、N-(3-胺丙基)嗎啉 (N-(3-aminopropyl)morpholine)、2-甲基哌嗪(2-methylpiperazine)、1-甲基哌嗪(1-methylpiperazine)、1-胺基-4-甲基哌嗪(1-amino-4-methylpiperazine)、1-苄基哌嗪(1-benzyl piperazine)、1-苯基哌嗪(1-phenyl piperazine)或前述之混合物。 Further, the aforementioned cyclic organic amine may include 1-(2-hydroxyethyl)piperazine (HEP), 1-(2-aminoethyl)piperazine (1-(2-) Aminoethyl)piperazine), 1-(2-hydroxyethyl)methylpiperazine, N-(3-aminopropyl)morpholine (N-(3-aminopropyl)morpholine), 2-methylpiperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine (1-amino) -4-methylpiperazine), 1-benzyl piperazine, 1-phenyl piperazine or a mixture of the foregoing.
該光阻剝離液組成物較佳可使用單乙醇胺(MEA)、1-(2-羥乙基)哌嗪(HEP)或前述之混合物作為有機胺類化合物。 As the photoresist stripping liquid composition, monoethanolamine (MEA), 1-(2-hydroxyethyl)piperazine (HEP) or a mixture of the foregoing may be preferably used as the organic amine compound.
該光阻剝離液組成物可包括N,N-二甲基丙醯胺(N,N-Dimethyl Propionamide,DMPA)作為另一溶劑，與丙酮縮甘油一同使用。前述N,N-二甲基丙醯胺溶劑具有優異的剝離效果，因此能取代N-甲基甲醯胺(N-methylformamide,NMF)、N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone,NMP)等等用於習知光阻剝離液組成物中的溶劑。前述溶劑能提供降低對環境以及人體危害的效果，且在清洗過程中不會造成光阻(PR)析出的問題，因此不會導致金屬腐蝕，反而具有優異的清洗性能。 The photoresist stripper composition may include N,N-Dimethyl Propionamide (DMPA) as another solvent and used together with acetone glycerol. The aforementioned N,N-dimethylpropanamide solvent has excellent peeling effect, and thus can replace N-methylformamide (NMF) and N-methyl-2-pyrrolidone (N-methyl-2). -pyrrolidone, NMP) and the like are used in the solvent of the conventional photoresist stripper composition. The foregoing solvent can provide an effect of reducing environmental and human hazards, and does not cause a problem of photoresist (PR) precipitation during the cleaning process, so that it does not cause metal corrosion, and has excellent cleaning performance.
在該光阻剝離液組成物中，前述N,N-二甲基丙醯胺的含量最好為10至90重量百分比(wt%)，較佳為15至75重量百分比(wt%)。以該光阻剝離液組成物的總量為基準，若該N,N-二甲基丙醯胺的含量低於10重量百分比(wt%)，光阻去除性能可能會降低；若該N,N-二甲基丙醯胺的含量高於90重量百分比(wt%)，該剝離液的清洗性能可能會降低。 In the resist stripper composition, the content of the aforementioned N,N-dimethylpropionamide is preferably from 10 to 90% by weight (wt%), preferably from 15 to 75% by weight (% by weight). Based on the total amount of the photoresist stripper composition, if the content of the N,N-dimethylpropionamide is less than 10% by weight (wt%), the photoresist removal performance may be lowered; if the N, The content of N-dimethylpropionamide is more than 90% by weight (wt%), and the cleaning performance of the stripper may be lowered.
並且，除了前述丙酮縮甘油以及前述N,N-二甲基丙醯胺以外，該光阻剝離液組成物可進一步包含一非質子極性溶劑。前述非 質子極性溶劑的作用在於將被前述胺類化合物剝離的高分子凝膠塊溶解成單元分子(unit molecule)。具體而言，其可避免在清洗過程中經常發生的光阻再附著問題。 Further, in addition to the aforementioned acetone glycerin and the aforementioned N,N-dimethylpropionamide, the photoresist stripper composition may further comprise an aprotic polar solvent. The aforementioned non The function of the protic polar solvent is to dissolve the polymer gel block peeled off by the aforementioned amine compound into a unit molecule. In particular, it avoids the problem of photoresist reattachment that often occurs during the cleaning process.
前述非質子極性溶劑可包括二甲基亞碸(dimethylsulfoxide)、N-甲基甲醯胺(N-methylformamide,NMF)、N-甲基吡咯烷酮(N-methyl-2-pyrrolidone,NMP)、N,N-二甲基乙醯胺(N,N-dimethylacetamide)、N,N-二甲基甲醯胺(N,N-dimethylformamide)、N,N-二甲基咪唑(N,N-dimethylimidazole)、γ-丁內酯(γ-butyrolactone)、環丁碸(sulfolane)、四氫呋喃甲醇(Tetrahydrofurfuryl alcohol,THFA)等等，前述溶劑可單獨使用或是可合併兩種或多種使用，最好，合併兩種或多種使用，但並不侷限於此。至於前述非質子極性溶劑，最好可使用N-甲基甲醯胺(NMF)、N-甲基吡咯烷酮(NMP)或前述的混合物。 The aforementioned aprotic polar solvent may include dimethylsulfoxide, N-methylformamide (NMF), N-methyl-2-pyrrolidone (NMP), N, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylimidazole, Γ-butyrolactone, sulfolane, tetrahydrofurfuryl alcohol (THFA), etc., the foregoing solvents may be used singly or in combination of two or more, preferably, two Or multiple uses, but not limited to this. As the aprotic polar solvent, it is preferred to use N-methylformamide (NMF), N-methylpyrrolidone (NMP) or a mixture of the foregoing.
以該光阻剝離液組成物的總量為基準，前述非質子極性溶劑的使用量最好為1至30重量百分比(wt%)。若該非質子極性溶劑的含量低於1重量百分比(wt%)，光阻去除性能可能會降低；若該非質子極性溶劑的含量高於30重量百分比(wt%)，可能會有金屬佈線腐蝕的問題。 The aprotic polar solvent is preferably used in an amount of from 1 to 30% by weight (% by weight) based on the total amount of the resist stripper composition. If the content of the aprotic polar solvent is less than 1% by weight (wt%), the photoresist removal performance may be lowered; if the content of the aprotic polar solvent is more than 30% by weight (wt%), there may be a problem of corrosion of the metal wiring. .
並且，該光阻剝離液組成物可進一步包含超純水。前述超純水可包括常規使用的超純水，並無特定限制。由於該光阻剝離液組成物可為水性(aqueous)或是非水性(non-aqueous)，因此前述超純水可視需求而適當地添加，並且，以該光阻剝離液組成物的總量為基準， 前述超純水的含量最好為1至40重量百分比(wt%)。 Also, the photoresist stripper composition may further comprise ultrapure water. The aforementioned ultrapure water may include ultrapure water which is conventionally used, and is not particularly limited. Since the photoresist stripping liquid composition may be aqueous or non-aqueous, the ultrapure water may be appropriately added as needed, and based on the total amount of the photoresist stripping liquid composition. , The aforementioned ultrapure water is preferably contained in an amount of from 1 to 40% by weight (% by weight).
並且，以該光阻剝離液組成物的總量為基準，該光阻剝離液組成物可進一步包含0.01至10重量百分比(wt%)的腐蝕抑制劑。前述腐蝕抑制劑的具體範例包括具有C1至C12烷基的沒食子酸烷基酯類(alkyl gallate)化合物；諸如巰基苯咪唑(mercaptobenzimidazole)、巰基甲基咪唑(mercaptomethylimidazole)等等的巰基類(mercapto)化合物；諸如甲基苯駢三氮唑(tolytriazole)、苯駢三氮唑(benzotriazole)、羧酸苯駢三氮唑(carboxylic benzotriazole)等等的***(triazole)類化合物；或前述的混合物，但並不侷限於此。 Further, the photoresist stripper composition may further contain 0.01 to 10% by weight (% by weight) of a corrosion inhibitor based on the total amount of the photoresist stripper composition. Specific examples of the foregoing corrosion inhibitor include an alkyl gallate compound having a C1 to C12 alkyl group; a mercapto group such as mercaptobenzimidazole, mercaptomethylimidazole, or the like ( a mercapto) compound; a triazole compound such as tolytriazole, benzotriazole, carboxylic benzotriazole, or the like; or the foregoing Mixture, but not limited to this.
此外，該光阻剝離液組成物可進一步包括已知常規用於提高剝離效果以及抗腐蝕性的添加劑，並無特定限制。前述添加劑的具體範例可包括沒食子酸甲酯(Methyl gallate)、五倍子酚(pyrogallol)、有機酸(organic acid)、醣類(saccharides)等等。更具體而言，前述有機酸可包括沒食子酸(gallic acid)、草酸(oxalic acid)、羥丁基二酸(malic acid)、抗壞血酸(ascorbic acid)等等，而前述醣類可包括山梨醇(sorbitol)等等。 Further, the photoresist stripper composition may further include an additive conventionally known for improving the peeling effect as well as corrosion resistance, and is not particularly limited. Specific examples of the aforementioned additives may include Methyl gallate, pyrogallol, organic acid, saccharides, and the like. More specifically, the aforementioned organic acid may include gallic acid, oxalic acid, malic acid, ascorbic acid, etc., and the aforementioned sugar may include sorbus Sorbitol and so on.
並且，該光阻剝離液組成物可廣泛地使用於塗料以及剝離工業領域。 Further, the photoresist stripper composition can be widely used in the field of coatings and peeling industries.
同時，依據本發明另一實施例，其提供一種光阻剝離方法，係使用前文描述的光阻剝離液組成物。 Meanwhile, according to another embodiment of the present invention, there is provided a photoresist stripping method using the photoresist stripping liquid composition described above.
如前文所述，本發明之發明人察覺到在習知光阻剝離液組成物中執行各種功能之乙二醇醚溶劑的問題，遂逐步研究能夠替代 前述乙二醇醚溶劑的物質，並完成了本發明的光阻剝離方法，其係使用具有與習知光阻剝離液組成物相同之優異剝離性能的光阻剝離液組成物，並可避免金屬佈線的腐蝕。 As described above, the inventors of the present invention have perceived the problem of performing a glycol ether solvent having various functions in a conventional photoresist stripping liquid composition, and a stepwise study can be substituted. The material of the glycol ether solvent described above, and the photoresist stripping method of the present invention is completed, which uses a photoresist stripping liquid composition having excellent peeling properties as the conventional photoresist stripping liquid composition, and can avoid metal wiring. corrosion.
由於乙二醇醚已被取代，因此本發明的光阻剝離方法很環保，同時，本發明的光阻剝離方法還展現出與習知剝離方法相同或是更為優異的光阻剝離效果以及抗腐蝕效果。 Since the glycol ether has been substituted, the photoresist stripping method of the present invention is environmentally friendly, and the photoresist stripping method of the present invention also exhibits the same or superior photoresist stripping effect and resistance as the conventional stripping method. Corrosion effect.
具體言之，本發明的光阻剝離液組成物可透過沉浸(dip)或是噴灑(spray)的形式在室溫(25℃)或是更高的溫度條件下使用，且其可使用超音波清洗裝置(ultrasonic cleaning device)等等的裝置來剝離光阻。 Specifically, the photoresist stripping liquid composition of the present invention can be used in the form of dip or spray at room temperature (25 ° C) or higher, and ultrasonic waves can be used. A device such as an ultrasonic cleaning device to strip the photoresist.
依據本發明，由於習知光阻剝離液組成物中使用之具危害性的乙二醇醚類溶劑已被取代，因此本發明能夠提供一種光阻剝離液組成物，其不會危害人體以及環境，具環保性，同時能展現出與習知光阻剝離液組成物相同或是更為優異的光阻剝離效果以及抗腐蝕效果。 According to the present invention, since the hazardous glycol ether solvent used in the conventional photoresist stripping liquid composition has been replaced, the present invention can provide a photoresist stripping liquid composition which does not harm the human body and the environment. It is environmentally friendly and exhibits the same or better photoresist peeling effect and corrosion resistance as the conventional photoresist stripper composition.
以下將透過具體的實施例進一步詳細說明本發明。然而，下述實施例僅用於闡明本發明，本發明的保護範圍並不侷限於下述實施例。 The invention will now be described in further detail by way of specific examples. However, the following examples are merely illustrative of the invention, and the scope of protection of the invention is not limited to the following examples.
利用下表1所示的組成成分和含量製備實施例1~5以及 比較例1~5的光阻剝離液組成物(單位：重量百分比(wt%))。 Examples 1 to 5 were prepared using the composition and content shown in Table 1 below. The photoresist stripping liquid compositions of Comparative Examples 1 to 5 (unit: weight percentage (wt%)).
DMPA：N,N-二甲基丙醯胺(N,N-Dimethyl Propionamide) DMPA: N,N-Dimethyl Propionamide
NMF：N-甲基甲醯胺(N-methylformamide) NMF: N-methylformamide
NMP：N-甲基吡咯烷酮(N-methylpyrrolidone) NMP: N-methylpyrrolidone
MDG：甲基二乙二醇(Methyl Diglycol)(同義名：二乙二醇單甲基醚(Diethylene Glycol Monomethyl Ether)) MDG: Methyl Diglycol (synonym: Diethylene Glycol Monomethyl Ether)
Solketal：(2,2-二甲基-1,3-二氧戊環-4-基)甲醇((2,2-dimethyl-1,3-dioxolan-4-yl)methanol)(同義名：亞異丙基甘油(Isopropylidene glycerol)) Solketal: (2,2-dimethyl-1,3-dioxolan-4-yl)methanol (synonym: sub Isopropylidene glycerol)
MEA：單乙醇胺(Monoethanol amine) MEA: Monoethanol amine
HEP：1-(2-羥乙基)哌嗪(1-(2-Hydroxyethyl)piperazine) HEP: 1-(2-hydroxyethyl)piperazine (1-(2-Hydroxyethyl) piperazine)
為了評價實施例1~5以及比較例1~5之光阻剝離液組成物的性能，進行以下的剝離測試和金屬腐蝕測試。 In order to evaluate the properties of the photoresist stripping liquid compositions of Examples 1 to 5 and Comparative Examples 1 to 5, the following peeling test and metal corrosion test were performed.
1.製造試片(測試剝離性能的試片)1. Manufacturing test piece (test piece for testing peeling performance)
使用旋轉(spin)或滑移(slip)裝置將目前使用的光阻劑(Dongjin Semichem有限公司供售，產品型號DTFR-N200)，在玻璃以及氮化矽(SiNx)的正面上塗覆厚度1微米，之後，使用加熱板或是烘箱使其在約150℃的溫度下硬化而製成試片。 The currently used photoresist (Dongjin Semichem Co., Ltd., product model DTFR-N200) is coated on the front side of glass and tantalum nitride (SiNx) by a thickness of 1 μm using a spin or slip device. Thereafter, a test piece was prepared by hardening at a temperature of about 150 ° C using a hot plate or an oven.
2.剝離性能測試2. Stripping performance test
將各實施例以及比較例的剝離液組成物置入噴塗裝置中，並加熱到50℃。然後，朝前述製備的試片噴灑前述剝離液組成物約1分鐘，接著用超純水清洗並用氮氣進行乾燥。透過肉眼以及顯微鏡觀察剝離情況，並將結果顯示於下表2中。 The stripping liquid compositions of the respective examples and comparative examples were placed in a spraying device and heated to 50 °C. Then, the stripping liquid composition was sprayed on the test piece prepared as described above for about 1 minute, followed by washing with ultrapure water and drying with nitrogen. The peeling was observed through the naked eye and a microscope, and the results are shown in Table 2 below.
X：光阻未被剝離 X: The photoresist is not stripped
△：部分光阻被剝離，但未溶解 △: Part of the photoresist was peeled off but not dissolved
O：光阻完全被剝離 O: The photoresist is completely stripped
經由上表2的結果可知，未使用危害人體以及環境之乙二醇醚類溶劑的實施例1~5的光阻剝離液組成物，與習知使用乙二醇醚類溶劑的比較例1~5的光阻剝離液組成物相比，能夠展現出相同或是更優異的光阻剝離效果。 From the results of the above Table 2, it is understood that the photoresist stripping liquid compositions of Examples 1 to 5 which are not harmful to human body and environmental glycol ether solvent are compared with the conventionally used glycol ether solvent. Compared with the photoresist stripper composition of 5, it can exhibit the same or more excellent photoresist stripping effect.
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| KR20170107162A (en) * | 2016-03-15 | 2017-09-25 | 동우 화인켐 주식회사 | Resist stripper composition |
| KR102153087B1 (en) * | 2016-09-29 | 2020-09-07 | 주식회사 엘지화학 | Composition for cleaning substrate of display device and preparing method of display device using the same |
| CN108424818A (en) * | 2017-02-14 | 2018-08-21 | 东友精细化工有限公司 | Cleaning masks liquid composition |
| CN107102517A (en) * | 2017-06-02 | 2017-08-29 | 合肥市惠科精密模具有限公司 | A kind of AMOLEED display screens remover composition with photoresist |
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| CN110846154A (en) * | 2019-08-30 | 2020-02-28 | 安徽富乐德科技发展有限公司 | Plate-attachment-preventing cleaning agent for OLED organic evaporation equipment and application |
| CN114730709A (en) | 2019-11-20 | 2022-07-08 | 日产化学株式会社 | Cleaning agent composition and cleaning method |
| CN111142341A (en) * | 2019-12-31 | 2020-05-12 | 江苏中德电子材料科技有限公司 | Environment-friendly high-stability aqueous photoresist stripping liquid for panels and preparation method thereof |
| CN111458990A (en) * | 2020-02-12 | 2020-07-28 | 惠州达诚微电子材料有限公司 | Photoresist stripping liquid for copper process of advanced panel |
| CN115469516B (en) * | 2022-11-03 | 2023-03-24 | 江苏奥首材料科技有限公司 | Stripping agent for III-V semiconductor compound photoresist, preparation method and application thereof |
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| KR100390567B1 (en) * | 2000-12-30 | 2003-07-07 | 주식회사 동진쎄미켐 | method of controlling photoresist stripping process and method of regenerating photoresist stripping composition using near infrared spectrometer |
| TWI276929B (en) * | 2003-12-16 | 2007-03-21 | Showa Denko Kk | Photosensitive composition remover |
| CN101223483B (en) * | 2005-07-19 | 2011-07-27 | 昭和电工株式会社 | Removing solution for photosensitive composition |
| JP4773562B2 (en) * | 2006-05-26 | 2011-09-14 | エルジー・ケム・リミテッド | Stripper composition for photoresist |
| US20080096785A1 (en) * | 2006-10-19 | 2008-04-24 | Air Products And Chemicals, Inc. | Stripper Containing an Acetal or Ketal for Removing Post-Etched Photo-Resist, Etch Polymer and Residue |
| WO2010090146A1 (en) * | 2009-02-03 | 2010-08-12 | 出光興産株式会社 | Resist remover composition and method for removing resist using same |
| CN101866118A (en) * | 2009-04-16 | 2010-10-20 | 巴斯夫公司 | Organic photoresist remover composition |
| JP5691273B2 (en) | 2009-07-23 | 2015-04-01 | Jnc株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| WO2011019189A2 (en) * | 2009-08-11 | 2011-02-17 | 동우 화인켐 주식회사 | Resist stripping solution composition, and method for stripping resist by using same |
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