TWI730913B - Resistor Stripping Liquid - Google Patents

Resistor Stripping Liquid Download PDF

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TWI730913B
TWI730913B TW109135483A TW109135483A TWI730913B TW I730913 B TWI730913 B TW I730913B TW 109135483 A TW109135483 A TW 109135483A TW 109135483 A TW109135483 A TW 109135483A TW I730913 B TWI730913 B TW I730913B
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cyclic amine
copper
amino acid
mass
molybdenum
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TW202121074A (en
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淵上真一郎
鈴木靖紀
鬼頭佑典
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日商松下知識產權經營股份有限公司
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
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Abstract

提供一種在銅/鉬的積層膜上將硬烘烤過的阻劑剝離時可抑制銅或鉬的底切之阻劑剝離液。此阻劑剝離液包括: 相對於剝離液總量為0.5〜5質量%的二級環胺;相對於前述二級環胺為5~10質量%的鹼性胺基酸;相對於前述鹼性胺基酸為10~30質量%的保護劑;相對於前述二級環胺為10〜50質量%的糖醇;有機極性溶劑;及水。 Provided is a resist stripping solution that can inhibit undercutting of copper or molybdenum when stripping hard-baked resists on a copper/molybdenum laminated film. This resist stripping solution includes: 0.5 to 5 mass% of the secondary cyclic amine relative to the total amount of the peeling liquid; 5 to 10 mass% of the basic amino acid relative to the aforementioned secondary cyclic amine; 10 to 30 relative to the aforementioned basic amino acid Mass% protective agent; 10-50 mass% sugar alcohol relative to the aforementioned secondary cyclic amine; organic polar solvent; and water.

Description

阻劑剝離液Resistor Stripping Liquid

本發明係有關於用來將在光微影(Photolithography)製程中所使用的光阻(Photoresist)剝離之阻劑(Resist)剝離液。The present invention relates to a resist stripping solution used to strip the photoresist used in the photolithography process.

目前已提出能夠提供例如4K、8K的高畫質之播放的傳輸格式,而且也已展開播放的測試。也相應地提供具有大螢幕的電視。液晶電視為目前電視的主流,與畫素對應的電晶體形成於用來作為大螢幕的透明基板(玻璃)上。上述的形成步驟使用了光微影技術。At present, transmission formats that can provide high-quality playback such as 4K and 8K have been proposed, and playback tests have also been launched. A TV with a large screen is also provided accordingly. LCD TVs are the mainstream of current TVs, and transistors corresponding to pixels are formed on a transparent substrate (glass) used as a large screen. The above-mentioned formation step uses photolithography technology.

由於螢幕尺寸的增加,有必要減少形成於透明基板上的導電部分的電阻。為此,使用了銅作為導電部分。銅具有高導電性。然而,對透明基板的附著力低。因此,使用了鉬作為透明基板與銅之間的底塗層。Due to the increase in screen size, it is necessary to reduce the resistance of the conductive portion formed on the transparent substrate. For this reason, copper is used as a conductive part. Copper has high conductivity. However, the adhesion to the transparent substrate is low. Therefore, molybdenum is used as an undercoat layer between the transparent substrate and the copper.

鉬係通常不易被腐蝕的金屬,但已知當鉬與銅形成兩層結構時,鉬會被顯著地腐蝕。Molybdenum is generally a metal that is not easily corroded, but it is known that when molybdenum and copper form a two-layer structure, molybdenum is significantly corroded.

專利文獻1公開了一種剝離液,對在鉬層上設置了銅層之兩層結構的兩層進行蝕刻之後,在剝離阻劑層的剝離液中使用包含2個以上的氮而不具有2級或3級的烷醇胺、和硫醇基及醯胺結構之胺基酸,因此能夠抑制鉬的腐蝕並將阻劑剝離。Patent Document 1 discloses a peeling solution. After etching two layers of a two-layer structure in which a copper layer is provided on a molybdenum layer, the peeling solution for peeling off the resist layer contains two or more nitrogens and does not have two levels. Or tertiary alkanolamine, and amino acid with thiol group and amide structure, so it can inhibit the corrosion of molybdenum and peel off the resist.

再者,專利文獻1的特徵還包括由於使用苯並三唑等的銅的腐蝕保護劑時會在銅表面上產生沉澱,因此不使用此腐蝕保護劑。Furthermore, the feature of Patent Document 1 also includes that since a copper corrosion protection agent such as benzotriazole is used, precipitation is generated on the copper surface, so this corrosion protection agent is not used.

另外,相較於提交專利文獻1時所使用的透明基板,目前所使用的透明基板更大。因此,在藉由光微影技術在大螢幕上形成元件的情況下,會執行嚴格的生產管理,不允許任何一個元件的故障。因此,會要求不可發生與蝕刻誤差直接相關之塗佈的光阻膜的剝離問題。結果,曝光前的光阻的烘烤處理(也稱為煅燒處理)的溫度有升高的傾向。 [現有技術文獻] [專利文獻] In addition, compared with the transparent substrate used at the time of filing Patent Document 1, the transparent substrate currently used is larger. Therefore, in the case of forming components on a large screen by photolithography technology, strict production management will be implemented, and failure of any component will not be allowed. Therefore, it is required that the coated photoresist film peeling problem that is directly related to the etching error should not occur. As a result, the temperature of the photoresist baking treatment (also referred to as calcination treatment) before exposure tends to increase. [Prior Art Literature] [Patent Literature]

[專利文獻1] 國際專利公開第2010/0738887號公報[Patent Document 1] International Patent Publication No. 2010/0738887

已知胺基酸係能夠強烈地腐蝕銅的物質。亦即,專利文獻1的剝離液係較低程度地使用腐蝕銅的胺類、和強烈地腐蝕銅的胺基酸,而並無使用銅的保護劑。然而,專利文獻1的剝離液抑制了銅的腐蝕也抑制了底塗層的鉬的腐蝕。It is known that amino acids can strongly corrode copper. That is, the peeling liquid system of Patent Document 1 uses amines that corrode copper and amino acids that strongly corrode copper to a low degree, and does not use a copper protective agent. However, the peeling liquid of Patent Document 1 suppresses the corrosion of copper and also the corrosion of molybdenum of the undercoat layer.

可認為其原因如以下所述。在使用剝離液時,氧在銅的表面上被還原。因此,電子從銅的表面供給至剝離液之側。此處,如果使用難以腐蝕銅的胺類,則電子會從鉬供給而不是從銅供給。因此,使得鉬被腐蝕。It is considered that the reason is as follows. When the stripping liquid is used, oxygen is reduced on the surface of the copper. Therefore, electrons are supplied from the surface of the copper to the side of the stripping liquid. Here, if amines that are hard to corrode copper are used, electrons are supplied from molybdenum instead of copper. Therefore, the molybdenum is corroded.

另一方面,此處,藉由同時使用腐蝕銅的胺基酸,使得電子也從銅放出,進而抑制鉬的腐蝕。亦即,係藉由難以腐蝕銅的烷醇胺將阻劑剝離,而產生於銅表面上用於還原作用的電子不僅從鉬供給也從銅本身供給之方法。On the other hand, here, by using an amino acid that corrodes copper at the same time, electrons are also released from copper, thereby suppressing the corrosion of molybdenum. That is, it is a method in which the resist is peeled off by alkanolamine, which is difficult to corrode copper, and the electrons generated on the copper surface for reduction are supplied not only from molybdenum but also from copper itself.

換言之,係藉由特意地腐蝕些許的銅層以保護鉬層的方法,亦為試圖利用烷醇胺與胺基酸之間的平衡以保護這兩層的方法。In other words, the method of protecting the molybdenum layer by deliberately etching a little copper layer is also a method of trying to use the balance between the alkanolamine and the amino acid to protect the two layers.

然而,相較於提交專利文獻1的時間點,目前在製程中的阻劑的煅燒溫度變高(硬烘烤),出現阻劑本身無法藉由烷醇胺剝離的狀況。因此,變得需要一種比烷醇胺更適合將硬烘烤後的阻劑分解之鹼性物質。 However, compared to the time when Patent Document 1 was filed, the calcination temperature of the current resist in the manufacturing process becomes higher (hard baking), and the resist itself cannot be peeled off by the alkanolamine. Therefore, there is a need for an alkaline substance that is more suitable for decomposing the resist after hard baking than alkanolamine.

再者,相對於畫素附近的導電部分具有比較細的圖案,來自於每個畫素的導電部分被整合於螢幕周圍的部分中,因此具有寬度大的圖案。 Furthermore, the conductive part near the pixel has a relatively thin pattern, and the conductive part from each pixel is integrated in the part around the screen, so it has a pattern with a large width.

如以上所述,在混合了寬度大的圖案和寬度小的圖案的狀態下使用強鹼時,會產生難以調整胺與胺基酸之間的平衡的問題。亦即,在此方法中,基本上在胺基酸少(胺多)時鉬被腐蝕,而在胺基酸多(胺少)時銅被腐蝕。然而,由於存在寬度大的圖案和寬度小的圖案兩者,因此可以取得胺基酸與胺之間的平衡的範圍變得非常狹窄,無法提供實質上取得平衡的剝離液。 As described above, when a strong base is used in a state where a pattern with a large width and a pattern with a small width are mixed, it is difficult to adjust the balance between the amine and the amino acid. That is, in this method, molybdenum is corroded when there are few amino acids (more amines), and copper is corroded when there are many amino acids (less amines). However, since there are both a pattern with a large width and a pattern with a small width, the range in which the balance between the amino acid and the amine can be achieved becomes very narrow, and it is impossible to provide a peeling liquid that is substantially balanced.

本發明係有鑑於上述的問題所構思的,本發明提供在充分地剝離硬烘烤後的光阻的同時不論在寬度大的圖案的部分還是在寬度小的圖案的部分都能夠抑制鉬及銅的腐蝕之阻劑剝離液。 The present invention is conceived in view of the above-mentioned problems. The present invention provides that molybdenum and copper can be suppressed both in the part of the pattern with a large width and the part of the pattern with a small width while sufficiently peeling off the photoresist after hard baking. The corrosion inhibitor stripping liquid.

因此,在本發明中,在使用環胺、和胺基酸的前提之下,使用銅保護劑。而且,對胺添加過量的胺基酸,以抑制鉬的腐蝕,並利用保護劑調整銅的腐蝕程度。 Therefore, in the present invention, under the premise of using cyclic amines and amino acids, a copper protective agent is used. In addition, an excessive amount of amino acid is added to the amine to inhibit the corrosion of molybdenum, and the degree of corrosion of copper is adjusted with a protective agent.

更具體而言,根據本發明的阻劑剝離液包括:相對於剝離液總量為0.5~5質量%的二級環胺;相對於前述二級環胺為5~10質量%的鹼性胺基酸;相對於前述鹼性胺基酸為10~30質量%的保護劑;相對於前述二級環胺為10~50質量%的糖醇;有機極性溶劑;和水;其中前述二級環胺係咪唑和哌啶中的至少一者。 More specifically, the resist stripping liquid according to the present invention includes: 0.5 to 5 mass% of the secondary cyclic amine relative to the total amount of the stripping liquid; 5 to 10 mass% of the basic amine relative to the aforementioned secondary cyclic amine Base acid; 10 to 30% by mass of protective agent relative to the aforementioned basic amino acid; 10 to 50% by mass of sugar alcohol relative to the aforementioned secondary cyclic amine; organic polar solvent; and water; wherein the aforementioned secondary ring At least one of amine-based imidazole and piperidine.

根據本發明的阻劑剝離液,在難以腐蝕銅、強鹼性的二級環胺中過量地混入強烈地腐蝕銅的鹼性胺基酸。如此一來,銅會被腐蝕,但可根據保護劑的量來調整銅的腐蝕程度。亦即,並非取得兩種腐蝕劑的平衡,而是藉由保護劑來抑制其中一種腐蝕劑的作用。因此,即使在存在寬度大的圖案和寬度小的圖案的情況下,也能夠將鉬的腐蝕及銅的腐蝕抑制於實際應用的範圍內。 According to the resist stripping solution of the present invention, an excessive amount of a basic amino acid that strongly corrodes copper is mixed in a secondary cyclic amine that is hard to corrode copper and is strongly alkaline. In this way, copper will be corroded, but the degree of corrosion of copper can be adjusted according to the amount of protective agent. That is, instead of achieving a balance between two corrosive agents, the protective agent is used to inhibit the effect of one of the corrosive agents. Therefore, even when there are patterns with a large width and a pattern with a small width, the corrosion of molybdenum and the corrosion of copper can be suppressed within the practical application range.

再者,由於混合了糖醇,因此也能夠抑制鉬與銅之間的腐蝕。 Furthermore, since sugar alcohol is mixed, it is also possible to suppress corrosion between molybdenum and copper.

而且,由於此剝離液的組成不包含無機的酸或無機的鹼,因此對鋁的導電部分也不會發生腐蝕。 Moreover, since the composition of the peeling liquid does not contain inorganic acids or inorganic bases, it does not corrode the conductive parts of aluminum.

以下對根據本發明的阻劑剝離液描述實施例並進行說明。另外,以下的說明描述了本發明的一實施形態及一實施例,而本發明並不限定於以下的說明。以下的說明在不脫離本發明的精神的情況下可以進行更改。再者,在以下的說明中,在表示範圍的情況下有時候會使用「~」,其意味著從「以上(等於且大於此值)至以下(等於且小於此值)」的意思。 Hereinafter, embodiments of the resist stripping liquid according to the present invention will be described and explained. In addition, the following description describes an embodiment and an example of the present invention, and the present invention is not limited to the following description. The following description can be modified without departing from the spirit of the present invention. Furthermore, in the following description, "~" is sometimes used to indicate a range, which means from "above (equal to and greater than this value) to less than (equal to and less than this value)".

根據本發明的阻劑剝離液包括二級環胺、鹼性胺基酸、有機極性溶劑、保護劑、水、和糖醇。 The resist stripping liquid according to the present invention includes a secondary cyclic amine, a basic amino acid, an organic polar solvent, a protective agent, water, and a sugar alcohol.

再者,本發明的目標對象係在鉬上積層銅了的導電部分。特別是混合了寬度為大約5~15μm厚的導電部分、和寬度為300~500μm厚的導電部分。而且,還存在由鋁所構成的導電部分。 Furthermore, the target object of the present invention is a conductive part in which copper is laminated on molybdenum. In particular, a conductive portion with a width of approximately 5 to 15 μm and a conductive portion with a width of 300 to 500 μm are mixed. Moreover, there are conductive parts made of aluminum.

鉬的厚度為大約30~50nm,而銅的厚度為400~800nm。鋁的部分則具有200~400nm的厚度。關於這些厚度,有必要介於在實際應用上不會出現鉬的底切(undercut)、銅的腐蝕、鋁的腐蝕的問題之範圍內。 The thickness of molybdenum is about 30-50nm, and the thickness of copper is 400-800nm. The aluminum part has a thickness of 200 to 400 nm. With regard to these thicknesses, it is necessary to be within a range in which problems of undercut of molybdenum, corrosion of copper, and corrosion of aluminum do not occur in practical applications.

再者,阻劑為正型的光阻,其包含酚醛清漆樹脂及重氮萘醌(Diazonaphthoquinone)。而且,以在150℃以上進行了煅燒處理的光阻作為目標對象。光阻通常在大約100℃的溫度下進行熱處理。因此,150℃以上的熱處理稱為高溫處理(硬烘烤)。 Furthermore, the resist is a positive photoresist, which includes a novolak resin and Diazonaphthoquinone (Diazonaphthoquinone). In addition, a photoresist that has been calcined at a temperature of 150°C or higher is targeted. The photoresist is usually heat-treated at a temperature of about 100°C. Therefore, heat treatment at 150°C or higher is called high temperature treatment (hard bake).

二級環胺適合使用咪唑(CAS編號:288-32-4)、哌啶(CAS編號:110-89-4)。咪唑及哌啶能夠剝離硬烘烤後的光阻。相對於剝離液的總量,二級環胺的含量以0.5~5質量%為佳,且以0.7~2.0質量%為較佳。 For secondary cyclic amines, imidazole (CAS number: 288-32-4) and piperidine (CAS number: 110-89-4) are suitable for use. Imidazole and piperidine can peel off the photoresist after hard baking. Relative to the total amount of the peeling liquid, the content of the secondary cyclic amine is preferably 0.5 to 5 mass%, and more preferably 0.7 to 2.0 mass%.

胺基酸可以使用鹼性胺基酸。其能強烈地溶解銅。以使用精胺酸和離胺酸為特佳。雖然組胺酸被分類為鹼性胺基酸,但用於根據本發明的阻劑剝離液時對於鉬的抗腐蝕不太具有效果。 As the amino acid, a basic amino acid can be used. It can strongly dissolve copper. It is particularly preferable to use arginine and lysine acid. Although histidine is classified as a basic amino acid, it is less effective for molybdenum corrosion resistance when used in the resist stripping liquid according to the present invention.

相對於環胺,胺基酸的含量為5~10質量%,以6~8質量%為佳。當換算成剝離液的總量時,則相當於0.025~0.5質量%。 The content of the amino acid relative to the cyclic amine is 5-10% by mass, preferably 6-8% by mass. When converted into the total amount of the peeling liquid, it is equivalent to 0.025 to 0.5% by mass.

保護劑為抑制胺基酸對銅的腐蝕的物質。具體而言,可為苯並三唑、5-甲基-1H-苯並三唑、2-巰基苯並咪唑、2-巰基苯並噻唑、2-巰基-5-甲基苯並咪唑、1-[N,N-雙(2-乙基己基)胺基甲基]-1H-苯並三唑、2,2'-[[((甲基-1H-苯並三唑-1-基)甲基]亞胺基]雙乙醇。因此,可由這些化合物所構成的群組中選出至少一種物質作為金屬表面保護劑。 The protective agent is a substance that inhibits the corrosion of copper by amino acids. Specifically, it can be benzotriazole, 5-methyl-1H-benzotriazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 1 -[N,N-bis(2-ethylhexyl)aminomethyl]-1H-benzotriazole, 2,2 ' -[[((methyl-1H-benzotriazol-1-yl) Methyl]imino]diethanol. Therefore, at least one substance can be selected from the group consisting of these compounds as the metal surface protective agent.

保護劑的量可調整為相對於鹼性胺基酸為10~30質量%。其相當於整個剝離液的0.0025~0.15質量%。如果保護劑的量相對於鹼性胺基酸而言為過多時,則銅的腐蝕被過度地抑制,使得鉬的腐蝕變多。然而,藉由將其含量設為介於上述的範圍內,不論導電部的寬度為大或小,都能夠適當地取得鉬的 腐蝕及銅的腐蝕之間的平衡。 The amount of the protective agent can be adjusted to 10 to 30% by mass relative to the basic amino acid. It is equivalent to 0.0025 to 0.15% by mass of the entire peeling liquid. If the amount of the protective agent is too large with respect to the basic amino acid, the corrosion of copper is excessively suppressed, and the corrosion of molybdenum increases. However, by setting its content within the above range, regardless of whether the width of the conductive portion is large or small, the molybdenum content can be appropriately obtained. The balance between corrosion and copper corrosion.

糖醇能夠防止鉬與銅之間的界線的腐蝕(稱為「銅的底切」)。適合使用甘油或山梨糖醇作為糖醇。相對於環胺,糖醇的含量以10~50質量%為佳。其相當於相對剝離溶液的總量為0.05~2.5質量%。 Sugar alcohol can prevent corrosion of the boundary between molybdenum and copper (called "undercutting of copper"). It is suitable to use glycerol or sorbitol as the sugar alcohol. Relative to the cyclic amine, the content of sugar alcohol is preferably 10-50% by mass. This corresponds to 0.05 to 2.5% by mass relative to the total amount of the peeling solution.

有機極性溶劑以非質子性有機溶劑為佳。質子性有機溶劑容易使得底塗層的鉬發生腐蝕。具體而言,有機極性溶劑,以二乙基甲醯胺、N-甲基甲醯胺、二甲基甲醯胺、N-甲基-2-吡咯烷酮、四氫呋喃、二甲基亞碸等為可適用。 The organic polar solvent is preferably an aprotic organic solvent. Protic organic solvents tend to corrode the molybdenum of the undercoat layer. Specifically, the organic polar solvent can be diethylformamide, N-methylformamide, dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, dimethyl sulfide, etc. Be applicable.

水的量適合為剝離液的總量的10~30質量%。再者,有機極性溶劑可為上述的環胺、水、保護劑及糖醇的殘留物。 The amount of water is suitably 10-30% by mass of the total amount of the peeling liquid. Furthermore, the organic polar solvent may be the residue of the aforementioned cyclic amine, water, protective agent, and sugar alcohol.

[實施例] [Example]

以下描述根據本發明的阻劑剝離液的實施例。製作出具有以下所示之組成的實施例及比較例的樣本剝離液,並對阻劑剝離用試驗片進行阻劑剝離試驗。 Hereinafter, examples of the resist stripping liquid according to the present invention will be described. The sample peeling liquids of the Examples and Comparative Examples having the composition shown below were prepared, and the resist peeling test was performed on the test piece for resist peeling.

<阻劑剝離用試驗片> <Test piece for resist peeling>

在玻璃基板上沉積厚度為30nm的鉬(Mo),並在其上積層厚度為500nm的銅(Cu)。再於其上積層厚度為300nm的SiN。將此稱為矽積層片。 Molybdenum (Mo) with a thickness of 30 nm was deposited on the glass substrate, and copper (Cu) with a thickness of 500 nm was laminated thereon. Then, a layer of SiN with a thickness of 300 nm was deposited on it. This is called a silicon laminate.

在矽積層片上的SiN層的預定位置處形成直徑為1μm的接觸窗孔(contact hole)。然後進一步積層厚度為30nm的鉬(Mo),並在其上積層厚度為500nm的銅(Cu)。 A contact hole with a diameter of 1 μm was formed at a predetermined position of the SiN layer on the silicon build-up layer sheet. Then, molybdenum (Mo) with a thickness of 30 nm was further laminated, and copper (Cu) with a thickness of 500 nm was laminated thereon.

接著,在最上層的銅層上塗佈正型的光阻,並在預定的溫度下煅燒(烘烤)。另外,通常會在150℃下進行大約2分鐘的高溫烘烤,然而為了確認阻劑剝離液的剝離力,在170℃下進行了5分鐘的烘烤。如此一來,阻劑膜進行了強烈的煅燒處理。在烘烤後,曝光出閘極(gate)線的圖案並顯影,然後蝕 刻上層的銅層及鉬層,以得到阻劑剝離用銅試驗片。 Next, a positive photoresist is coated on the uppermost copper layer, and fired (baked) at a predetermined temperature. In addition, high-temperature baking is usually carried out at 150°C for about 2 minutes, but in order to confirm the peeling force of the resist stripping solution, baking was carried out at 170°C for 5 minutes. As a result, the resist film has undergone a strong calcination treatment. After baking, the gate line pattern is exposed and developed, and then etched The upper copper layer and molybdenum layer are carved to obtain a copper test piece for resist peeling.

亦即,在阻劑剝離用銅試驗片中,具有蝕刻了閘極線的圖案之鉬層及銅層,且其上沉積了煅燒處理後的阻劑膜。再者,此阻劑膜也覆蓋接觸窗孔部分。 That is, in the copper test piece for resist peeling, the molybdenum layer and the copper layer in which the gate line pattern was etched were provided, and the resist film after a calcination process was deposited on it. Furthermore, this resist film also covers the contact hole portion.

再者,在矽積層片上沉積厚度為500nm的鋁(Al),並以與阻劑剝離用銅試驗片相同的方式在鋁層蝕刻出閘極線的圖案。阻劑層的煅燒處理也同樣在170℃下進行5分鐘。如以上所述以得到阻劑剝離用鋁試驗片。 Furthermore, aluminum (Al) was deposited with a thickness of 500 nm on the silicon build-up sheet, and the gate line pattern was etched on the aluminum layer in the same manner as the copper test piece for resist stripping. The calcination treatment of the resist layer was similarly performed at 170°C for 5 minutes. As described above, an aluminum test piece for resist peeling was obtained.

<評估> <evaluation>

作為評估將阻劑剝離的能力(以下稱為「剝離力」),利用加溫至40℃的各種剝離液對各個試驗片進行40秒的處理,並使用光學顯微鏡確認阻劑的殘留狀態。然後,將在表面上明顯殘留有阻劑的情況評估為「×」(表示不合格或失敗的意思),而若在沒有發生問題的狀態下將阻劑剝離則評估為「○」(表示合格或成功的意思)。 As an evaluation of the ability to peel the resist (hereinafter referred to as "peel force"), each test piece was treated with various peeling solutions heated to 40°C for 40 seconds, and the remaining state of the resist was confirmed using an optical microscope. Then, the case where the resist is obviously remaining on the surface is evaluated as "×" (means unqualified or failed), and if the resist is peeled off without problems, it is evaluated as "○" (means pass Or the meaning of success).

再者,作為評估抑制金屬表面的腐蝕(以下稱為「金屬損傷」)的能力,將試驗片浸入40℃的樣本剝離液中進行4分鐘的處理之後,使用SEM(Scanning Electron Microscope)觀察試驗片的金屬膜的腐蝕狀態。在上述觀察中,以表面放大視角及剖面視角觀察被蝕刻的部分。 In addition, to evaluate the ability to inhibit corrosion of the metal surface (hereinafter referred to as "metal damage"), the test piece was immersed in a sample stripping solution at 40°C for 4 minutes, and then the test piece was observed using SEM (Scanning Electron Microscope) The corrosion state of the metal film. In the above observation, the etched part was observed with a magnified surface view angle and a cross-sectional view angle.

在表面放大視角中,確認銅層及鋁層的表面的腐蝕狀態。特別是確認閘極線的表面及接觸窗孔的邊緣部上的銅的狀態。再者,在剖面視角中,確認被蝕刻後的金屬層的傾斜面的粗糙狀態、傾斜角及銅的底切。 In the magnified view of the surface, the corrosion state of the surface of the copper layer and the aluminum layer was confirmed. In particular, check the state of the copper on the surface of the gate line and the edge of the contact hole. Furthermore, in the cross-sectional view, the roughness, the inclination angle, and the copper undercut of the inclined surface of the etched metal layer were confirmed.

然後,在各個視角中,將被判斷為製造不合格的狀態評估為「x」(表示不合格或失敗的意思),並將被判斷為製造合格的狀態評估為「○」(表示合格或成功的意思)。 Then, in each perspective, the state judged as unqualified manufacturing is evaluated as "x" (meaning unqualified or failed), and the state judged as qualified as manufacturing is evaluated as "○" (representing qualified or successful the meaning of).

<樣本剝離液> <Sample Stripping Solution>

以下記載了各種樣本剝離液的組成。有時候也會使用以下的縮寫表示以下的各種化合物。咪唑:IZ(CAS編號:288-32-4)、哌啶:PIP(CAS編號:110-89-4)、二乙基甲醯胺:DEF(CAS編號:617-84-5)、N-甲基甲醯胺:NMF(CAS編號:123-39-7)、二甘醇單丁醚:BDG(CAS編號:112-34-5)、2,2'-[[[(甲基-1H-苯並三唑-1-基)甲基]亞胺基]雙乙醇:MBET(CAS編號:88477-37-6)、N-甲基-2-吡咯烷酮:NMP(CAS編號:872-50-4)、哌嗪:PIZ(CAS編號:110-85-0)、N-甲基乙醇胺:MMA(CAS編號:109-83-1)。5-甲基苯並三唑:5M-BTA(CAS編號:136-85-6)、精胺酸:Arg(CAS編號:74-79-3)、離胺酸:Lys(CAS編號:70-54-2)、組胺酸:His(CAS編號:71-00-1)、甘油:Glycerol(CAS編號:56-81-5)、山梨糖醇:Stol(CAS編號:50-70-4)。 The composition of various sample stripping solutions is described below. The following abbreviations are sometimes used to indicate the following various compounds. Imidazole: IZ (CAS number: 288-32-4), piperidine: PIP (CAS number: 110-89-4), diethylmethamide: DEF (CAS number: 617-84-5), N- Methyl formamide: NMF (CAS number: 123-39-7), diethylene glycol monobutyl ether: BDG (CAS number: 112-34-5), 2,2'-[[[(methyl-1H -Benzotriazol-1-yl)methyl]imino]diethanol: MBET (CAS number: 88477-37-6), N-methyl-2-pyrrolidone: NMP (CAS number: 872-50- 4) Piperazine: PIZ (CAS number: 110-85-0), N-methylethanolamine: MMA (CAS number: 109-83-1). 5-Methylbenzotriazole: 5M-BTA (CAS Number: 136-85-6), Arginine: Arg (CAS Number: 74-79-3), Lysine: Lys (CAS Number: 70- 54-2), Histidine: His (CAS Number: 71-00-1), Glycerol: Glycerol (CAS Number: 56-81-5), Sorbitol: Stol (CAS Number: 50-70-4) .

(實施例1) (Example 1)

使用以下的組成製備出實施例1的樣本剝離液。 The sample peeling liquid of Example 1 was prepared using the following composition.

1.0g作為環胺化合物的IZ、0.07g作為胺基酸的Arg(相對於環胺化合物為7質量%)、0.01g作為保護劑的MBET(相對於胺基酸為14.3質量%)、0.30g作為糖醇的Glycerol(相對於環胺化合物為30質量%)、71.62g作為極性溶劑的NMP、27.0g的水,將以上成分混合作為實施例1的樣本。 1.0g of IZ as a cyclic amine compound, 0.07g of Arg as an amino acid (7% by mass relative to the cyclic amine compound), 0.01g of MBET as a protective agent (14.3% by mass relative to the amino acid), 0.30g Glycerol as a sugar alcohol (30% by mass relative to the cyclic amine compound), 71.62 g of NMP as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Example 1.

(實施例2) (Example 2)

使用以下的組成製備出實施例2的樣本剝離液。 The sample peeling liquid of Example 2 was prepared using the following composition.

4.0g作為環胺化合物的IZ、0.32g作為胺基酸的Arg(相對於環胺化合物為8質量%)、0.09g作為保護劑的MBET(相對於胺基酸為28.1質量%)、1.60g作為糖醇的Glycerol(相對於環胺化合物為40質量%)、 66.99g作為極性溶劑的DEF、27.0g的水,將以上成分混合作為實施例2的樣本。 4.0g of IZ as a cyclic amine compound, 0.32g of Arg as an amino acid (8% by mass relative to the cyclic amine compound), 0.09g of MBET as a protective agent (28.1% by mass relative to the amino acid), 1.60g Glycerol as a sugar alcohol (40% by mass relative to the cyclic amine compound), 66.99 g of DEF as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Example 2.

(實施例3) (Example 3)

使用以下的組成製備出實施例3的樣本剝離液。 The sample peeling liquid of Example 3 was prepared using the following composition.

1.0g作為環胺化合物的PIP、0.07g作為胺基酸的Arg(相對於環胺化合物為7質量%)、0.01g作為保護劑的MBET(相對於胺基酸為14.3質量%)、0.30g作為糖醇的Glycerol(相對於環胺化合物為30質量%)、71.62g作為極性溶劑的DEF、27.0g的水,將以上成分混合作為實施例3的樣本。 1.0g of PIP as a cyclic amine compound, 0.07g of Arg as an amino acid (7% by mass relative to the cyclic amine compound), 0.01g of MBET as a protective agent (14.3% by mass relative to the amino acid), 0.30g Glycerol as a sugar alcohol (30% by mass with respect to the cyclic amine compound), 71.62 g of DEF as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Example 3.

(實施例4) (Example 4)

使用以下的組成製備出實施例4的樣本剝離液。 The sample peeling liquid of Example 4 was prepared using the following composition.

4.0g作為環胺化合物的PIP、0.32g作為胺基酸的Arg(相對於環胺化合物為8質量%)、0.09g作為保護劑的5M-BTA(相對於胺基酸為28.1質量%)、1.60g作為糖醇的Glycerol(相對於環胺化合物為40質量%)、66.99g作為極性溶劑的NMF、27.0g的水,將以上成分混合作為實施例4的樣本。 4.0 g of PIP as a cyclic amine compound, 0.32 g of Arg as an amino acid (8% by mass relative to the cyclic amine compound), 0.09 g of 5M-BTA as a protective agent (28.1% by mass relative to the amino acid), 1.60 g of Glycerol as a sugar alcohol (40% by mass relative to the cyclic amine compound), 66.99 g of NMF as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Example 4.

(實施例5) (Example 5)

使用以下的組成製備出實施例5的樣本剝離液。 The sample peeling liquid of Example 5 was prepared using the following composition.

3.0g作為環胺化合物的PIP、0.21g作為胺基酸的Arg(相對於環胺化合物為7質量%)、0.03g作為保護劑的MBET(相對於胺基酸為14.3質量%)、0.90g作為糖醇的Stol(相對於環胺化合物為30質量%)、 68.86g作為極性溶劑的DEF、27.0g的水,將以上成分混合作為實施例5的樣本。 3.0 g of PIP as a cyclic amine compound, 0.21 g of Arg as an amino acid (7% by mass relative to the cyclic amine compound), 0.03 g of MBET as a protective agent (14.3% by mass relative to the amino acid), 0.90 g Stol as a sugar alcohol (30% by mass relative to the cyclic amine compound), 68.86 g of DEF as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Example 5.

(實施例6) (Example 6)

使用以下的組成製備出實施例6的樣本剝離液。 The sample peeling liquid of Example 6 was prepared using the following composition.

1.0g作為環胺化合物的PIP、0.07g作為胺基酸的Lys(相對於環胺化合物為7質量%)、0.01g作為保護劑的MBET(相對於胺基酸為14.3質量%)、0.10g作為糖醇的Glycerol(相對於環胺化合物為10質量%)、71.82g作為極性溶劑的NMP、27.0g的水,將以上成分混合作為實施例6的樣本。 1.0g of PIP as a cyclic amine compound, 0.07g of Lys as an amino acid (7% by mass relative to the cyclic amine compound), 0.01g of MBET as a protective agent (14.3% by mass relative to the amino acid), 0.10g Glycerol as a sugar alcohol (10% by mass relative to the cyclic amine compound), 71.82 g of NMP as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Example 6.

(比較例1) (Comparative example 1)

使用以下的組成製備出比較例1的樣本剝離液。 The sample peeling liquid of Comparative Example 1 was prepared using the following composition.

1.0g作為環胺化合物的IZ、0.03g作為胺基酸的Arg(相對於環胺化合物為3質量%)、0.006g作為保護劑的MBET(相對於胺基酸為20質量%)、0.30g作為糖醇的Glycerol(相對於環胺化合物為30質量%)、71.664g作為極性溶劑的NMP、27.0g的水,將以上成分混合作為比較例1的樣本。 1.0g of IZ as a cyclic amine compound, 0.03g of Arg as an amino acid (3% by mass relative to the cyclic amine compound), 0.006g of MBET as a protective agent (20% by mass relative to an amino acid), 0.30g Glycerol as a sugar alcohol (30% by mass relative to the cyclic amine compound), 71.664 g of NMP as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Comparative Example 1.

(比較例2) (Comparative example 2)

使用以下的組成製備出比較例2的樣本剝離液。 The sample peeling liquid of Comparative Example 2 was prepared using the following composition.

4.0g作為環胺化合物的IZ、0.60g作為胺基酸的Arg(相對於環胺化合物為15質量%)、0.18g作為保護劑的MBET(相對於胺基酸為30質量%)、1.60g作為糖醇的Glycerol(相對於環胺化合物為40質量%)、 66.62g作為極性溶劑的DEF、27.0g的水,將以上成分混合作為比較例2的樣本。 4.0 g of IZ as a cyclic amine compound, 0.60 g of Arg as an amino acid (15% by mass relative to the cyclic amine compound), 0.18 g of MBET as a protective agent (30% by mass relative to the amino acid), 1.60 g Glycerol as a sugar alcohol (40% by mass relative to the cyclic amine compound), 66.62 g of DEF as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Comparative Example 2.

(比較例3) (Comparative example 3)

使用以下的組成製備出比較例3的樣本剝離液。 The sample peeling liquid of Comparative Example 3 was prepared using the following composition.

1.0g作為環胺化合物的PIP、0.07g作為胺基酸的Arg(相對於環胺化合物為7質量%)、0.003g作為保護劑的MBET(相對於胺基酸為4.3質量%)、0.30g作為糖醇的Glycerol(相對於環胺化合物為30質量%)、71.627g作為極性溶劑的DEF、27.0g的水,將以上成分混合作為比較例3的樣本。 1.0g of PIP as a cyclic amine compound, 0.07g of Arg as an amino acid (7% by mass relative to the cyclic amine compound), 0.003g of MBET as a protective agent (4.3% by mass relative to the amino acid), 0.30g Glycerol as a sugar alcohol (30% by mass relative to the cyclic amine compound), 71.627 g of DEF as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Comparative Example 3.

(比較例4) (Comparative Example 4)

使用以下的組成製備出比較例4的樣本剝離液。 The sample peeling liquid of Comparative Example 4 was prepared using the following composition.

4.0g作為環胺化合物的PIP、0.32g作為胺基酸的Arg(相對於環胺化合物為8質量%)、0.10g作為保護劑的5M-BTA(相對於胺基酸為31質量%)、1.60g作為糖醇的Glycerol(相對於環胺化合物為40質量%)、66.98g作為極性溶劑的NMF、27.0g的水,將以上成分混合作為比較例4的樣本。 4.0 g of PIP as a cyclic amine compound, 0.32 g of Arg as an amino acid (8% by mass relative to the cyclic amine compound), 0.10 g of 5M-BTA as a protective agent (31% by mass relative to the amino acid), 1.60 g of Glycerol as a sugar alcohol (40% by mass relative to the cyclic amine compound), 66.98 g of NMF as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Comparative Example 4.

(比較例5) (Comparative Example 5)

使用以下的組成製備出比較例5的樣本剝離液。 The sample peeling liquid of Comparative Example 5 was prepared using the following composition.

1.0g作為環胺化合物的PIZ、0.07g作為胺基酸的Arg(相對於環胺化合物為7質量%)、0.01g作為保護劑的MBET(相對於胺基酸為14.3質量%)、0.30g作為糖醇的Glycerol(相對於環胺化合物為30質量%)、 71.62g作為極性溶劑的DEF、27.0g的水,將以上成分混合作為比較例5的樣本。 1.0g of PIZ as a cyclic amine compound, 0.07g of Arg as an amino acid (7% by mass relative to the cyclic amine compound), 0.01g of MBET as a protective agent (14.3% by mass relative to the amino acid), 0.30g Glycerol as a sugar alcohol (30% by mass relative to the cyclic amine compound), 71.62 g of DEF as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Comparative Example 5.

(比較例6) (Comparative Example 6)

使用以下的組成製備出比較例6的樣本剝離液。 The sample peeling liquid of Comparative Example 6 was prepared using the following composition.

1.0g作為環胺化合物的MMA、0.07g作為胺基酸的Lys(相對於環胺化合物為7質量%)、0.01g作為保護劑的MBET(相對於胺基酸為14.3質量%)、0.10g作為糖醇的Glycerol(相對於環胺化合物為10質量%)、71.82g作為極性溶劑的NMP、27.0g的水,將以上成分混合作為比較例6的樣本 1.0g MMA as a cyclic amine compound, 0.07g Lys as an amino acid (7% by mass relative to the cyclic amine compound), 0.01g MBET as a protective agent (14.3% by mass relative to the amino acid), 0.10g Glycerol as a sugar alcohol (10% by mass relative to the cyclic amine compound), 71.82 g of NMP as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Comparative Example 6.

(比較例7) (Comparative Example 7)

使用以下的組成製備出比較例7的樣本剝離液。 The sample peeling liquid of Comparative Example 7 was prepared using the following composition.

3.0g作為環胺化合物的IZ、0.21g作為胺基酸的Lys(相對於環胺化合物為7質量%)、0.03g作為保護劑的MBET(相對於胺基酸為14.3質量%)、0.00g作為糖醇的Glycerol(不含糖醇)、69.76g作為極性溶劑的NMP、27.0g的水,將以上成分混合作為比較例7的樣本。 3.0g IZ as a cyclic amine compound, 0.21g Lys as an amino acid (7% by mass relative to the cyclic amine compound), 0.03g MBET as a protective agent (14.3% by mass relative to the amino acid), 0.00g Glycerol as a sugar alcohol (without sugar alcohol), 69.76 g of NMP as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Comparative Example 7.

(比較例8) (Comparative Example 8)

使用以下的組成製備出比較例8的樣本剝離液。 The sample peeling liquid of Comparative Example 8 was prepared using the following composition.

1.0g作為環胺化合物的PIP、0.07g作為胺基酸的Arg(相對於環胺化合物為7質量%)、0.01g作為保護劑的MBET(相對於胺基酸為14.3質量%)、0.30g作為糖醇的Glycerol(相對於環胺化合物為30質量%)、 71.62g作為極性溶劑的BDG、27.0g的水,將以上成分混合作為比較例8的樣本。 1.0g of PIP as a cyclic amine compound, 0.07g of Arg as an amino acid (7% by mass relative to the cyclic amine compound), 0.01g of MBET as a protective agent (14.3% by mass relative to the amino acid), 0.30g Glycerol as a sugar alcohol (30% by mass relative to the cyclic amine compound), 71.62 g of BDG as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Comparative Example 8.

(比較例9) (Comparative Example 9)

使用以下的組成製備出比較例9的樣本剝離液。 The sample peeling liquid of Comparative Example 9 was prepared using the following composition.

1.0g作為環胺化合物的PIP、0.07g作為胺基酸的His(相對於環胺化合物為7質量%)、0.01g作為保護劑的MBET(相對於胺基酸為14.3質量%)、0.30g作為糖醇的Glycerol(相對於環胺化合物為30質量%)、71.62g作為極性溶劑的DEF、27.0g的水,將以上成分混合作為比較例9的樣本。 1.0g of PIP as a cyclic amine compound, 0.07g of His as an amino acid (7% by mass relative to the cyclic amine compound), 0.01g of MBET as a protective agent (14.3% by mass relative to the amino acid), 0.30g Glycerol as a sugar alcohol (30% by mass relative to the cyclic amine compound), 71.62 g of DEF as a polar solvent, 27.0 g of water, and the above components were mixed as a sample of Comparative Example 9.

製備上述的樣本剝離液,並進行剝離試驗。關於實施例的樣本剝離液的組成及剝離試驗的結果如表1所示,而關於比較例的樣本剝離液的組成及剝離試驗的結果如表2及表3所示。 Prepare the above-mentioned sample stripping solution and conduct a stripping test. The composition of the sample peeling liquid of the Example and the results of the peeling test are shown in Table 1, and the composition of the sample peeling liquid of the Comparative Example and the results of the peeling test are shown in Tables 2 and 3.

[表1]

Figure 02_image001
[Table 1]
Figure 02_image001

[表2]

Figure 02_image003
[Table 2]
Figure 02_image003

[表3]

Figure 02_image005
[table 3]
Figure 02_image005

參照表1,為本發明的組合物之實施例1至實施例6,能夠在40℃、40秒的處理條件下,將在170℃、5分鐘的條件下施加了熱處理之阻劑膜剝離。 因此,將剝離力評估為「〇」。再者,在藉由SEM觀察時,閘極線及接觸窗孔中的銅膜也具有良好的狀態,故亦將金屬損傷評估為「〇」。再者,針對由於鉬的腐蝕所引起的底切和鉬與銅之間的銅的底切也評估為「〇」。 此外,鋁層的剝離力亦評估為「〇」。另外,關於鋁,在實施例及比較例中都沒有發生問題。Refer to Table 1, which are Examples 1 to 6 of the composition of the present invention. The resist film that has been heat-treated at 170°C for 5 minutes can be peeled off at 40°C for 40 seconds. Therefore, the peeling force was evaluated as "〇". Furthermore, when observed by SEM, the copper film in the gate line and the contact hole was also in a good state, so the metal damage was also evaluated as "o". Furthermore, the undercut due to corrosion of molybdenum and the undercut of copper between molybdenum and copper were also evaluated as "o". In addition, the peeling force of the aluminum layer was also evaluated as "〇". In addition, regarding aluminum, no problem occurred in the Examples and Comparative Examples.

另一方面,比較例1及比較例2係胺基酸過少的情況(比較例1)和過多的情況(比較例2)。當胺基酸過少時會發生鉬的底切。這是因為無法適當地腐蝕銅膜的緣故。另一方面,當胺基酸過多時銅的表面會被腐蝕。On the other hand, Comparative Example 1 and Comparative Example 2 are cases where there are too few amino acids (Comparative Example 1) and cases where there are too many amino acids (Comparative Example 2). When the amino acid is too low, undercutting of molybdenum occurs. This is because the copper film cannot be corroded properly. On the other hand, when there are too many amino acids, the surface of copper will be corroded.

再者,比較例3及比較例4係保護劑過少的情況(比較例3)和過多的情況(比較例4)。當保護劑過少時無法防止胺基酸對銅膜的腐蝕。另一方面,當保護劑過多時,銅表面不會被腐蝕,而會發生鉬的腐蝕(底切)。In addition, Comparative Example 3 and Comparative Example 4 are the case where the protective agent is too little (Comparative Example 3) and the case where it is too much (Comparative Example 4). When the protective agent is too small, the corrosion of the copper film by the amino acid cannot be prevented. On the other hand, when the protective agent is too much, the copper surface will not be corroded, but corrosion of molybdenum (undercut) will occur.

在比較例5中,胺係哌嗪。雖然哌嗪為環狀胺,但無法剝離硬烘烤過的阻劑膜。比較例6係以N-甲基乙醇胺(鏈烷醇胺)取代胺的情況,然而在這種情況下,也無法剝離硬烘烤過的阻劑膜。In Comparative Example 5, the amine is piperazine. Although piperazine is a cyclic amine, it cannot peel off the hard-baked resist film. In Comparative Example 6, N-methylethanolamine (alkanolamine) was substituted for the amine. However, in this case, the hard-baked resist film could not be peeled off.

比較例7係不添加糖醇的情況。在這種情況下,鉬與銅之間發生腐蝕,且發生了銅的底切(在表中以「Cu U.C.」表示)。Comparative Example 7 is a case where no sugar alcohol is added. In this case, corrosion occurred between molybdenum and copper, and undercutting of copper occurred (indicated by "Cu U.C." in the table).

比較例8係將為質子性有機溶劑的二甘醇單丁醚作為極性溶劑的情況。當將有機極性溶劑質子化時,容易發生鉬的底切。Comparative Example 8 is a case where diethylene glycol monobutyl ether, which is a protic organic solvent, is used as a polar solvent. When the organic polar solvent is protonated, undercutting of molybdenum easily occurs.

比較例9係使用組胺酸作為胺基酸的情況。雖然組胺酸屬於鹼性胺基酸,但發生了鉬的底切。在根據本發明的剝離液的組合物中,可認為組胺酸對銅的腐蝕性低於離胺酸和精胺酸。Comparative Example 9 is a case where histidine is used as the amino acid. Although histidine is a basic amino acid, undercutting of molybdenum occurs. In the composition of the stripping liquid according to the present invention, it can be considered that histidine is less corrosive to copper than lysine and arginine.

如以上所述,在藉由光微影技術形成由鉬、銅及鋁所構成的佈線時,根據本發明的阻劑剝離液能夠抑制由於鉬和銅的腐蝕所引起的表面粗糙和底切。 [產業上的可利性] As described above, when a wiring composed of molybdenum, copper, and aluminum is formed by photolithography, the resist stripping solution according to the present invention can suppress surface roughness and undercuts caused by corrosion of molybdenum and copper. [Industrial Profitability]

本發明能夠適用於大面積的顯示裝置的製造過程中的阻劑剝離步驟。The present invention can be applied to the resist peeling step in the manufacturing process of a large-area display device.

無。no.

無。no.

Claims (4)

一種阻劑剝離液,包括:相對於剝離液總量為0.5~5質量%的二級環胺;相對於前述二級環胺為5~10質量%的鹼性胺基酸;相對於前述鹼性胺基酸為10~30質量%的保護劑;相對於前述二級環胺為10~50質量%的糖醇;有機極性溶劑;以及水;其中前述二級環胺係咪唑和哌啶中的至少一者。 A resist stripping liquid, comprising: 0.5 to 5 mass% of secondary cyclic amine relative to the total amount of the stripping liquid; 5 to 10 mass% of basic amino acid relative to the aforementioned secondary cyclic amine; relative to the aforementioned alkali The amino acid is 10-30% by mass of the protective agent; the sugar alcohol is 10-50% by mass relative to the aforementioned secondary cyclic amine; the organic polar solvent; and water; wherein the aforementioned secondary cyclic amine is imidazole and piperidine At least one of. 如請求項1所述之阻劑剝離液,其中前述鹼性胺基酸包含精胺酸和離胺酸中的至少一者。 The resist stripping liquid according to claim 1, wherein the basic amino acid includes at least one of arginine and lysine. 如請求項1所述之阻劑剝離液,其中前述保護劑係選自苯並三唑、5-甲基-1H-苯並三唑、2-巰基苯並咪唑、2-巰基苯並噻唑、2-巰基-5-甲基苯並咪唑、1-[N,N-雙(2-乙基己基)胺基甲基]-1H-苯並三唑、2,2'-[[(甲基-1H-苯並三唑-1-基)甲基]亞胺基]雙乙醇中的至少一者。 The resist stripping solution according to claim 1, wherein the aforementioned protective agent is selected from the group consisting of benzotriazole, 5-methyl-1H-benzotriazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-Mercapto-5-methylbenzimidazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-1H-benzotriazole, 2,2'-[[(methyl -1H-benzotriazol-1-yl)methyl]imino]diethanol. 如請求項1所述之阻劑剝離液,其中前述糖醇係甘油和山梨糖醇中的至少一者。The resist stripping liquid according to claim 1, wherein the sugar alcohol is at least one of glycerin and sorbitol.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007100086A (en) * 2005-09-30 2007-04-19 Rohm & Haas Electronic Materials Llc Release agent
JP2012060050A (en) * 2010-09-13 2012-03-22 Fujifilm Corp Cleaning composition, cleaning method using the same, and method of manufacturing semiconductor element
WO2016151645A1 (en) * 2015-03-24 2016-09-29 パナソニックIpマネジメント株式会社 Resist stripping liquid
TW201814036A (en) * 2016-09-30 2018-04-16 日商松下知識產權經營股份有限公司 Resist removal liquid

Family Cites Families (3)

* Cited by examiner, † Cited by third party
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JP6112446B2 (en) * 2012-10-31 2017-04-12 パナソニックIpマネジメント株式会社 Photoresist stripping composition
TWI691412B (en) * 2014-06-04 2020-04-21 日商琳得科股份有限公司 Air-resistive laminate, method for manufacturing the same, element for electronic device, and electronic device
JP6922957B2 (en) * 2015-09-30 2021-08-18 ブラザー工業株式会社 Liquid discharge device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007100086A (en) * 2005-09-30 2007-04-19 Rohm & Haas Electronic Materials Llc Release agent
JP2012060050A (en) * 2010-09-13 2012-03-22 Fujifilm Corp Cleaning composition, cleaning method using the same, and method of manufacturing semiconductor element
WO2016151645A1 (en) * 2015-03-24 2016-09-29 パナソニックIpマネジメント株式会社 Resist stripping liquid
TW201814036A (en) * 2016-09-30 2018-04-16 日商松下知識產權經營股份有限公司 Resist removal liquid

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