201224140 六、發明說明: 【發明所屬之技術領域】 本發明係關於光阻剝除劑之組成,尤其是關於可用於 TFT-LCD製造之所有過程巾的顧的光關_之組成。 【先前技術】 在平面顯tfII(FPD)之製造過程巾,光刻過程廣泛用來在基板 上形成預疋的圖案。光刻過程包括一系列的過程,有曝光過程、 乾絲或濕制程,及灰化顧。在光刻·中,將光阻塗在基板 上,而後曝光,再實施乾蝕或濕触過程,則可形成一圖案。在此 過程中’可阻剝除劑去除殘留在基板之金屬線上的光阻。 目前’ LCD製造過程巾所使賴光阻_敝狀部分是初 級或次級胺與極性溶劑或乙二醇的無水的有機化合物。一般而 言,在侧雌之後殘留的光阻_使用上面所賴絲剝除劑 來去除’之後’再以水來清洗基板。在此情況下,會有一些問題 產生’即金屬線被舰,且光阻劑再次黏附到基板上而產生雜質。 其原因是,若醇贿核合,會產生絲(氫氧基)離子,後者對金 屬’例如!g ’魏高的顧性。為此緣故’需使用特別的腐餘抑 棚來防止金麟的雜。<#:而,傳統的雜抑綱有其缺點, 即昂貴且無效率。尤其是近年來,平面顯示器面板像lcDs的 製造,因為必須使用腐蝕抑制劑而使生產費用增加。 此外對於TFT-LCDA1佈線膜之情形,必須將改良的光阻刺 由佈線膜上嫌掉。若使闕齡胺,縣_無法被完全剝除, 因為胺去除光阻劑之能力較低。韓國專利N〇川必5^779中揭露 201224140 光阻剝除劑之組成,其含有弱鹼性醇胺的三級醇胺。但,此組 成會產生―問題,即其無法完全去除改良的光阻劑。 同時,若使用被水活化的強驗性醇胺,則其必會傷害到A1及 Cu佈線膜。為了避免此問題,傳統的^^製造過程所用的有機 ^阻剥除溶液含有非常少4的触抑侧。然*,在tft_lcd製 w過私中錢用含水的光阻剝除溶液聰除溶液巾的水會隨時 門&加而揮發’因此’齡溶液中的水含量纽變,而腐触抑制 齊1的腐麵抑制能力及剝除溶液的光阻剝除的能力也隨之快速改 變。為此緣故’有許多關於LCD製造過程所使_含有強驗性醇 ^及腐懈卩麵眺告被發表,但_咖製造擁所使用含有 強驗性醇_含水的光關除_報告,雜少看到。 因此,本發明之目的係要解決上面所述之問題,本發明發展 出—較穩定的且可抑制餘及剝除光阻的喊,該組成含有一腐 飿抑制劑’其係含♦基化合物的疏基群。 【發明内容】 本發明之目的係要提供用於TFT_LCD製造過程十的含 制除劑’其包含—含絲化合物的縣群之__,其中 唾基化合物可防止Cu及A1钱 、 持光阻剝除的能力。 仏量改變時,㈣ _為== 造=,-特徵,本發軸職 一的極性有機奪一二 201224140 依據本發明之一實施例,所提供關於LCD製造過程中的光阻 剝除組成,其中之初級醇胺係由單乙醇胺、單異丙醇胺、氨基 曱基小丙醇、2_曱基氨基乙醇、及3_氨基丙醇胺中選取一個^更 多個。 依據本發明之另一實施例,所提供用於LCD製造過程中的光 阻剝除組成,其中之酒精係由乙二醇、1-己醇、辛醇、丨_庚醇、卜 癸醇、2-庚醇、及四氫糠基酒精中選取一個或更多個。 依據本發明之另一實施例,所提供用於LCD製造過程中的光 阻剝除組成,其中之腐蝕抑制劑是C5_cl〇之雜環,該雜 個或更多個選自N、0、及S的雜原子,且該雜環之碳原子被疏基 所取代。 依據本發明之另一實施例,所提供用於LCD製造過程中的光 阻剝除組成,其中之雜環是咪唑。 依據本發明之另一實施例,所提供用kLCD製造過程中的光 阻剝除組成,其巾之雜抑棚係自2_祕苯料、2,5—二疏基 塞二唑、及2_巯基苯噻唑中選取一個或更多個。 依據本發明之另一實施例,所提供用於LCD製造過程中的光 阻剝除組成’其中的極性有鄭容劑包含乙二醇,該乙二醇之結構 :子式為R-0(CH2CH20)H,其中’ R係線性碳氫,或是分支的碳 氫’或是環狀碳氫。 依據本發明之另一實施例,所提供用MLCD製造過程中的光 阻剝除組成,其巾的錄有機溶_由NUb各細、 環丁砜、二曱基亞砜(DMS〇)、二甲基乙醯胺(DMAC)、及單曱基 曱酿胺中選取一個或更多個。 201224140 剝除—特徵’所提供_cd製造過財的光阻 精.w,⑻㈣加%的初級醇胺;⑼1〇-6〇心的酒 精,及(c)5-70wt%的極性有機溶劑。 剝除=本ΓΓ—實施例’所提供用於LCD製造過程中的光阻 允除、、且成,其中之初級醇胺是2_氨基_2_甲基丙醇。 依據本發权另-實關,所提供用於LCD製造過程中的光 阻剝除組成,其中之酒精係由乙二醇、L己醇、辛醇q•庚醇、^ 癸醇、2-庚醇、及四氫糠基酒精中選取一個或更多個。 【實施方式】 關於依據本發明之光阻剝除組成中之成份,其中含唾基化合 物之Μ基群被用來做為雜抑制劑,其量為組成總重量的請: 若腐餘抑制劑之含量在組成中太少,則對金屬佈線膜腐蚀的 防止功效就非常低,甚至抑制效果將更迅速減少。另—方面若 組成中之腐_侧的含量太多,則將減弱組成的光阻剝除能 力本發明之發明人已發現到,本發明之組成含有3讀^的腐餘抑 制劑時’就有足夠的能力來防止賴,且可剝除光阻劑。然而, 因為腐财卩侧昂#,就衫賴抑棚的含量增加到大於 所需的量。 而且,為了進一步增強對LCD圖案之成份的Mo、a卜及Cu 的随能力’其他的顧抑制劑也可添加入組成中。此外,包含 在。本發明之組成中的初級或次級醇胺具有u或更大的pH值(依 10%水溶液而論),故其在組成中之含量可以是㈣惑。醇胺的 例子包括單乙醇胺(MEA)、單異丙醇胺(MJpA)、2·曱基氨基乙醇 201224140 (2-MAE)、二乙基乙醇胺(DEE〇A)、以及 mdea、mdma、及 DEEOA中二個或更多個的混合物。而且,組成物中水的含量可以 是❹.1-50^/0,組成中酒精(例如,乙二醇(EG);沸點:197.7。〇 之含量可以是10-60 wt%。使用於本發明之組成中的極性有機溶劑 可以由N-曱基吡咯烷酮(nmr)、二甲基亞砜(DMs〇)、二甲基乙酰 胺(DMAC)、及N-甲基甲酰胺(NMF)中選取一個’或二個或更多個 的混合物’且其含量可以是組成總重量的5_5〇加%。此外,為了 在組成使用剝除光阻劑之後,方便洗淨光阻劑’可在組成中添加 20-60wt%的乙二醇’該乙二醇係由二乙二醇單乙哪dg)、二乙 二醇單T_DG)、三乙二醇驗(TEG)中選取—個,或二個或更多 個的混合物。較佳地、組成中乙二醇的含量是5_5_%。若組成 :乙二醇之含量太低,職不易溶解乾燥的光_,另一方面, 若乙二醇之含量太高,則其會增加組成的成本。 具有11或更大的PH值及150 t或更高的沸點的初級醇胺, 其含量在組成齡量愤佳的是㈣娜。若她_在組成中 之含量少於丨wt%,則在剝除過程進行中,組成對改良的光阻劑的 剝除能力將下降。若組成中初級醇胺之含量大㈣心,則需辦 力口賴抑侧的添加量’且會造成金屬佈軸的顧,並增加组曰 成的製造成本。組成中水的含量較佳是α㈣_,而且 t成中之酒精具有15G °c或更高的沸點,其例子包括乙二醇(EG. 彿點:197.7 °C)、及四氫糠基酒精⑽A;彿點.η , 中酒精的含量較佳是10_60wt%。若 )、、且成201224140 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to the composition of a photoresist stripping agent, and more particularly to the composition of all of the process wipes that can be used in the manufacture of TFT-LCDs. [Prior Art] In the manufacturing process of planar display tfII (FPD), a photolithography process is widely used to form a pre-twisted pattern on a substrate. The lithography process consists of a series of processes, including exposure, dry or wet processes, and ashing. In photolithography, a photoresist is applied to a substrate and then exposed, and then a dry or wet touch process is performed to form a pattern. During this process, the stripper removes the photoresist remaining on the metal lines of the substrate. At present, the LCD manufacturing process towel is made of a photoresist or a water-free organic compound of a primary or secondary amine with a polar solvent or ethylene glycol. In general, the photoresist remaining after the female side is removed by using the above-mentioned stripping agent to remove the 'after' and then the substrate is washed with water. In this case, there will be some problems that arise, that is, the wire is wounded by the ship, and the photoresist is again adhered to the substrate to generate impurities. The reason for this is that if the alcohol is bribed, it will produce silk (hydroxyl) ions, which are of concern to the metal ', for example, !g'. For this reason, it is necessary to use a special rot to prevent Jinlin's miscellaneous. <#: However, the traditional hybrid has its shortcomings, that is, it is expensive and inefficient. Especially in recent years, flat panel displays have been manufactured like lcDs because of the necessity of using corrosion inhibitors to increase production costs. Further, in the case of the TFT-LCDA1 wiring film, the improved photoresist must be smothered by the wiring film. If the ageing amine is used, the county cannot be completely stripped because the amine has a lower ability to remove the photoresist. The Korean patent N〇川必5^779 reveals the composition of the 201224140 photoresist stripping agent, which contains a tertiary alkanolamine of a weakly basic alkanolamine. However, this component creates the problem that it cannot completely remove the improved photoresist. At the same time, if a strong alcoholamine activated by water is used, it will damage the A1 and Cu wiring films. In order to avoid this problem, the organic resist stripping solution used in the conventional manufacturing process contains very few 4 suppressive sides. However, in the tft_lcd system, the water is removed from the solution with a water-containing photoresist. The water in the solution towel will be added at any time and then volatilized. Therefore, the water content in the solution is changed, and the corrosion is inhibited. The ability of the surface to inhibit the corrosion of the strip and the stripping of the stripping solution is also rapidly changed. For this reason, there are a lot of reports about the LCD manufacturing process, including the use of strong alcohols and rots, but the use of strong alcohols containing _ water-containing _ reports, See the miscellaneous. Accordingly, the object of the present invention is to solve the above-mentioned problems, and the present invention has developed a relatively stable and suppressable residual and stripping photoresist, the composition comprising a rot-inhibiting agent The base group. SUMMARY OF THE INVENTION The object of the present invention is to provide a detergent-containing agent for the TFT_LCD manufacturing process, which comprises a group of silk-containing compounds, wherein the salivation compound prevents Cu and A1 money, and holds photoresist. The ability to strip. When the amount of change is changed, (4) _ is == 造=,-characteristic, the polarity of the present invention is one or two. 201224140 According to an embodiment of the present invention, the photoresist stripping composition in the LCD manufacturing process is provided, The primary alcohol amine is selected from the group consisting of monoethanolamine, monoisopropanolamine, aminoguanidinylpropyl alcohol, 2-nonylaminoethanol, and 3-aminopropanolamine. According to another embodiment of the present invention, there is provided a photoresist stripping composition for use in an LCD manufacturing process, wherein the alcohol is ethylene glycol, 1-hexanol, octanol, hydrazine-heptanol, diterpene alcohol, One or more of 2-heptanol and tetrahydrofurfuryl alcohol are selected. According to another embodiment of the present invention, there is provided a photoresist stripping composition for use in an LCD manufacturing process, wherein the corrosion inhibitor is a heterocyclic ring of C5_cl〇, the hetero or more selected from the group consisting of N, 0, and a hetero atom of S, and the carbon atom of the hetero ring is substituted by a sulfhydryl group. According to another embodiment of the present invention, there is provided a photoresist stripping composition for use in an LCD manufacturing process, wherein the heterocycle is imidazole. According to another embodiment of the present invention, there is provided a photoresist stripping composition in the process of manufacturing a kLCD, and the shed of the towel is from 2 _ benzene, 2,5-dioxadioxazole, and 2 One or more of _mercaptobenzothiazole is selected. According to another embodiment of the present invention, there is provided a photoresist stripping composition for use in an LCD manufacturing process, wherein the polarity of the positive agent comprises ethylene glycol, and the structure of the ethylene glycol: the sub-form is R-0 ( CH2CH20)H, where 'R is a linear hydrocarbon, or a branched hydrocarbon' or a cyclic hydrocarbon. According to another embodiment of the present invention, there is provided a photoresist stripping composition in the manufacturing process of MLCD, wherein the organic solvent of the towel is prepared by NUB fine, sulfolane, dimethyl sulfoxide (DMS), dimethyl One or more of acetaminophen (DMAC) and monoterpene enamel amine are selected. 201224140 Stripping-Features provided by _cd made of photo-resistance fine. w, (8) (d) plus % of primary alcohol amine; (9) 1 〇-6 heart alcohol, and (c) 5-70% by weight of polar organic solvent. Stripping = This is the photoresistance provided in the LCD manufacturing process, and wherein the primary alcoholamine is 2-amino-2-methylpropanol. According to the present disclosure, the photoresist stripping composition provided in the LCD manufacturing process is provided by ethylene glycol, L-hexanol, octanol q-heptanol, decyl alcohol, 2- One or more of heptanol and tetrahydrofurfuryl alcohol are selected. [Embodiment] Regarding the composition of the photoresist stripping composition according to the present invention, the sulfhydryl group-containing thiol group is used as a hetero-inhibitor, and the amount thereof is the total weight of the composition: if the residual inhibitor If the content is too small in composition, the effect of preventing corrosion of the metal wiring film is very low, and even the suppression effect is more rapidly reduced. On the other hand, if the content of the rot on the side of the composition is too large, the photoresist stripping ability of the composition will be weakened. The inventors of the present invention have found that when the composition of the present invention contains a residual inhibitor of 3 readings, There is enough ability to prevent the razor and strip the photoresist. However, because of the rot of the affluent side, the content of the shed is increased to more than the required amount. Moreover, in order to further enhance the Mo, a, and Cu ability of the components of the LCD pattern, other inhibitors may be added to the composition. Also included. The primary or secondary alcoholamine in the composition of the present invention has a pH of u or more (in terms of a 10% aqueous solution), so its content in the composition may be (4). Examples of the alcoholamines include monoethanolamine (MEA), monoisopropanolamine (MJpA), thioglycolaminoethanol 201224140 (2-MAE), diethylethanolamine (DEE® A), and mdea, mdma, and DEEOA. a mixture of two or more. Moreover, the content of water in the composition may be 1.1-50^/0, the composition of the alcohol (for example, ethylene glycol (EG); boiling point: 197.7. The content of cerium may be 10-60 wt%. Used in this The polar organic solvent in the composition of the invention may be selected from N-mercaptopyrrolidone (nmr), dimethyl sulfoxide (DMs), dimethylacetamide (DMAC), and N-methylformamide (NMF). One 'or a mixture of two or more' and its content may be 5_5 〇 plus % of the total weight of the composition. In addition, in order to use the stripping photoresist after the composition is used, it is convenient to wash the photoresist 'in the composition Adding 20-60% by weight of ethylene glycol, which is selected from diethylene glycol monoethylene (dg), diethylene glycol mono-T_DG), triethylene glycol (TEG), or two A mixture of more or more. Preferably, the content of ethylene glycol in the composition is 5_5_%. If the composition: the content of ethylene glycol is too low, the job is not easy to dissolve the dry light _, on the other hand, if the content of ethylene glycol is too high, it will increase the cost of the composition. A primary alcohol amine having a pH of 11 or more and a boiling point of 150 t or more is inferior in compositional age (4). If her content in the composition is less than 丨wt%, the stripping ability of the composition for the improved photoresist will decrease during the stripping process. If the content of the primary alcoholamine in the composition is large (four), the addition amount of the side of the pressure-relief side is required, and the metal cloth axis is taken into consideration, and the manufacturing cost of the group is increased. The content of water in the composition is preferably α(tetra)_, and the alcohol in t is a boiling point of 15 G °c or higher, and examples thereof include ethylene glycol (EG. Foshan point: 197.7 ° C), and tetrahydrofurfuryl alcohol (10) A. The content of alcohol in the Buddha's point η is preferably 10_60% by weight. If ), and
且成中酒精之含量太少,則組 ^對Cu佈賴之脑的防止能力會下降。 L 含量太高’則會引起Ai金屬線的腐餘,且減少組成剝除Γ劑之 201224140 功效。此外’若酒精不加入組成中,不會影響到組成對腐飯抑制 及光阻翻除的能力,但由棚除系統有4G。€蚊高的剝除過程 溫度,故在剝除過程中,組成中之水會因内部氣體之壓力而造成 揮發,故會縮短剝除組成的預期壽命。因此緣故,在剝除纟且成使 用於LCD光_除過辦,需要麟錢#的量的崎添加入剝 除組成中。 依據本發明之光關除組·_含水的水溶驗成。在含水 之水溶液組成巾’胺之雖姐在有機獅組成巾更活化。 為此緣故’縱使在較低的溫度下,水雜齡組成去除在平面顯 不器製造過程巾,實施紐、植人及硬烤之後所殘留的改良的光 阻劑的能力,仍遠大於使用於LCD製造過程中傳統的有機剝除细 成的能力。較低的過程溫度可減少平面顯示面㈣製造成本。此 外’因為本發明的剝除組成含有最適度的腐财卩制劑,故可施用 於銘佈線及銅佈線,且也可使驗有顧形成触及c〇A過程 之中。 而且’本發明之剝除組成含有一種或多種的乙二醇,其可有 效地促進光__除。組成中的乙二醇可幫助溶解的光阻劑在 剝除組成中的擴散,因此可促進光_迅速的去除。組成甲的乙 二醇具有r_0(CH2CH2〇)h之結構分子式,其中r代表線性碳氣, 分枝碳氫’或是環狀碳氫。 更特別的是’由二乙醇單㈣(MDG)、二乙二醇單乙醚 (EDG)—乙—醇單丁醚⑽⑺、及三乙二醇驗(咖)中選取一個 或更多個來使用做為乙二醇。 本發明組射乙二狀含錄佳是购wt%。使胁組成中 201224140 之乙二醇可岐由具有上❹_Q(CH2CH20)H之構造分子式的乙 二醇中選取-個或二個或更多個的混合物。 同時,在驗性初級醇胺中,具空間位阻的域基_2_曱基小 丙醇(以下稱為amp)可被加人含有騎而不含水的錢剝除組成 中使得組成在不使用腐飯抑制劑之情況下,仍可防止…及仏 佈線的顧,且可完全齡改㈣光_,因為AMP是初級胺, 其會與水依下_反應方程式⑴反應喊生會腐齡屬佈線膜的 OH離子。在沒有水存树,胺與金屬間會發生依下面反應方程式 (2)之腐贼應。軸AMp是初_,其可抑烟做應,因為下 面的方程式(2)中所示之R非常大會引起空間位阻。此外,因為 AMP疋強驗性初級胺,其有利於對改良的光阻劑的剝除。 (1) 胺與銅在水溶液中之腐蝕性反應 RNH2 + H20 — RNH3+ + 0H-Cu2+ + 20H、Cu(0HMs)And if the content of alcohol in the middle is too small, the ability to prevent the brain of Cu will be reduced. If the L content is too high, it will cause the corrosion of the Ai wire and reduce the 201224140 effect of the composition of the stripping agent. In addition, if alcohol is not added to the composition, it will not affect the ability of the composition to suppress the rice and the photoresist is removed, but the shed removal system has 4G. The high temperature of the mosquito stripping process, so in the stripping process, the water in the composition will be volatilized due to the pressure of the internal gas, thus shortening the life expectancy of the stripping composition. For this reason, it is necessary to add it to the stripping composition when stripping the crucible and using it for the LCD light. According to the light-off group of the present invention, water-soluble water-soluble test. In the aqueous aqueous solution, the towel 'amine' is more activated in the organic lion composition towel. For this reason, even at lower temperatures, the water-age composition is removed in the flat-panel manufacturing process, and the ability to perform improved photoresist after the new, implanted, and hard-baked is still far greater than The ability of traditional organic stripping in the LCD manufacturing process. Lower process temperatures reduce the manufacturing cost of the flat display surface (IV). Further, since the stripping composition of the present invention contains the most suitable rot-cured bismuth preparation, it can be applied to the wiring of the inscription and the copper wiring, and the inspection can be made to touch the c〇A process. Further, the stripping composition of the present invention contains one or more kinds of ethylene glycol, which can effectively promote the removal of light. The ethylene glycol in the composition aids in the diffusion of the dissolved photoresist in the stripping composition and thus promotes light_rapid removal. The ethylene glycol constituting the methyl group has a structural formula of r_0(CH2CH2〇)h, wherein r represents a linear carbon gas, a branched hydrocarbon, or a cyclic hydrocarbon. More specifically, 'use one or more of diethanol mono (tetra) (MDG), diethylene glycol monoethyl ether (EDG) - ethyl alcohol monobutyl ether (10) (7), and triethylene glycol test (coffee) to use As ethylene glycol. In the present invention, the group B is in the form of a wt%. The ethylene glycol of 201224140 may be selected from a mixture of ethylene glycol having a structural formula of the upper ❹Q(CH2CH20)H, or a mixture of two or more. At the same time, in the test primary alcoholamine, the sterically hindered domain group 2_ fluorenyl glycerol (hereinafter referred to as amp) can be added to the composition without the water to remove the composition so that the composition is not In the case of using a rice cooker inhibitor, it is still possible to prevent ... and the 仏 wiring, and can be completely changed (4) light _, because AMP is a primary amine, which will react with the water-dependent reaction equation (1) It is an OH ion of the wiring film. In the absence of water, there is a relationship between the amine and the metal that occurs according to the following reaction equation (2). The axis AMp is the initial _, which suppresses the smoke, because the R shown in the following equation (2) causes a steric hindrance. In addition, because AMP is a strong primary amine, it facilitates the stripping of improved photoresists. (1) Corrosive reaction of amine and copper in aqueous solution RNH2 + H20 — RNH3+ + 0H-Cu2+ + 20H, Cu(0HMs)
Cu(OH)2 ⑻ + 4RNH3、[Cu(RNh2)4] (2) 胺與銅在有機溶液中之腐蝕性反應 Cu2+ + 4RNH2 Cu(RNH2)42 因此’依據本發明所提供的光阻剝除組成,在tft_lcd光阻 剝除過程中,縱使有水的存在,其亦具有優異的防止銅與銘佈線 之腐蝕的能力。此外,本發明之組成亦具有優異的去除光刻過程 實施後殘留的改良的光阻劑的能力。因此,本發明之組成可克服 傳統的剝除組成的缺點,而同時仍保有傳統的組成的優點。 此外,在半導體裝置及平面顯示面板之製造過程中,依據本 發明的光阻剝除組成具有去除光刻過程實施後所殘留的改良的光 201224140 阻劑的優異能力,其可使用於鋁及銅之佈線,亦可使用於有機模 开>成過程及COA過程中。當本發明之組成使用於含有沸點15〇 或更高的酒精與水之混合物中時,其防止腐蝕的能力可被提高, 且其預期壽命也可被增加。 本發明將參考例子更詳細地說明如下。然而,需了解到,這 些例子僅用來做為說明,不可被用來限制本發明之範圍。 例1 為了評估本發明之光阻剝除組成之性能,下面之方法被用來 測試對改良的光阻劑的剝除能力及防止腐蝕之能力。剝除組成含 有1 wt%的2-巯基苯咪唑做為腐蝕抑制劑,及其它成份。組成之 含量(wt%)顯示於下面的表丨中。玻璃基板上有A1佈線膜形成在 其上面,光阻劑尚未被去除,在16〇之爐中熱處理1〇分鐘熱 處理過之基板浸入50 〇C之剝除組成中30秒之後,被用來評估改 良的光阻劑被去除之程度。 此外,有Cu佈線膜形成其上的玻璃基板被浸入5〇 之剝除 組成10分鐘之後,被用來評估Cu佈線膜被腐蝕之程度。另使用 一具有Cu佈線膜之玻璃基板,其被浸入丙酮中1〇分鐘用來做為 評估之控制對照(表U。 依據下面之標準來評估測試結果,而評估結果顯示於下面的 表1中: [剝除A1線上改良光阻劑(PR)之能力] ◎:改良的光阻劑完全被去除; △:殘留微量的改良的光阻劑;及 X:殘留1/3或更多的改良的光阻劑 201224140Cu(OH)2(8) + 4RNH3, [Cu(RNh2)4] (2) Corrosive reaction of amine with copper in organic solution Cu2+ + 4RNH2 Cu(RNH2)42 Therefore 'resistance stripping provided in accordance with the present invention Composition, in the tft_lcd photoresist stripping process, even if there is water, it also has excellent ability to prevent corrosion of copper and Ming wiring. In addition, the composition of the present invention also has an excellent ability to remove the improved photoresist remaining after the lithography process is performed. Therefore, the composition of the present invention overcomes the disadvantages of the conventional stripping composition while still retaining the advantages of the conventional composition. In addition, in the manufacturing process of the semiconductor device and the flat display panel, the photoresist stripping composition according to the present invention has an excellent ability to remove the improved light 201224140 resist remaining after the photolithography process is performed, which can be used for aluminum and copper. The wiring can also be used in the organic mold opening process and the COA process. When the composition of the present invention is used in a mixture containing alcohol and water having a boiling point of 15 Torr or higher, its ability to prevent corrosion can be improved, and its life expectancy can also be increased. The present invention will be described in more detail with reference to examples as follows. However, it is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the invention. EXAMPLE 1 In order to evaluate the performance of the photoresist stripping composition of the present invention, the following method was used to test the stripping ability and corrosion resistance of the improved photoresist. The stripping composition contained 1 wt% of 2-mercaptobenazole as a corrosion inhibitor, and other ingredients. The composition (wt%) of the composition is shown in the following table. An A1 wiring film was formed thereon on the glass substrate, and the photoresist was not removed. The substrate was heat-treated in a 16-inch furnace for 1 minute. The heat-treated substrate was immersed in a stripping composition of 50 〇C for 30 seconds, and was used for evaluation. The extent to which the improved photoresist is removed. Further, the glass substrate on which the Cu wiring film was formed was immersed in a 5 Å stripping composition for 10 minutes, and was used to evaluate the extent to which the Cu wiring film was etched. Another glass substrate having a Cu wiring film which was immersed in acetone for 1 minute was used as a control control for evaluation (Table U. The test results were evaluated according to the following criteria, and the evaluation results are shown in Table 1 below. : [The ability to strip the modified photoresist (PR) on the A1 line] ◎: The improved photoresist is completely removed; △: A trace amount of the improved photoresist; and X: A modification of 1/3 or more of the residue Photoresist 201224140
腐飾之程度;I 〇·腐餘程度相同於控制基板的; 〇:犋厚相同於控制基板的,及,可忽略的表面腐蝕; △•膜厚比控制基板的小,及,發生表面腐敍;及 X:銅佈線膜被腐蝕,以致於膜厚減少了 1/2或更多。 [表1] 組成號 碼 胺的種 類 胺 (wt%) 水 (wt% ) EG (wt%) THFA (wt%) NMP (5%) +EDG (48%) (wt%) 剝除 A1線 上PR 之能 力 銅線 上之 腐触 1 MEA 7 20 20 53 ◎ ◎ 2 MEA 7 20 - 20 53 ◎ ◎ 3 MIPA 7 20 20 53 ◎ ◎ 4 MIPA 7 20 - 20 53 ◎ ◎ 5 DIPA 7 20 20 53 Δ ◎ 6 DIPA 7 20 - 20 53 Δ ◎ 7 TIPA 7 20 20 53 X ◎ 8 TIPA 7 20 - 20 53 X ◎ 9 2-MAE 7 20 - 20 53 ◎ ◎ 10 2-MAE 7 20 20 - 53 ◎ ◎ 12 201224140 11 MDEO A 7 20 20 - 53 X 12 MDEO A 7 20 20 53 X ◎ 13 DEEO A 7 20 20 53 X ◎ 14 DEEO A 7 20 - 20 53 X ◎ 15 AEEO A 7 20 20 - 53 Δ ◎ 16 AEEO A 7 20 - 20 53 Δ ◎ 17 3-APN 7 20 20 53 ◎ ◎ 18 3-APN 7 20 20 53 ◎ ◎ 註解: MEA:單乙醇胺 MIPA:單異丙醇胺 DIPA:二異丙醇胺 TIPA:三異丙醇胺 AMP: 2-氣基-2-曱基-1-丙醉 2-MAE:2-(曱基氨基)乙醇 MDEOA:曱基二乙醇胺 DEEOA:二乙基乙醇胺 13 201224140 AEEOA.氣基乙基乙醇胺 3-APN: 3-氨基丙醇胺 MDEA:甲基二乙醇胺 MDMA:曱基二甲醇胺 EG:二乙醇 EDG:二乙二醇單乙醚 NMP:N-曱基吡咯烷_ THFA:四氫糠基酒精 MBI:2-酼基苯咪唑 如上面表1中所看到的,本發明之組成包含2-疏基苯咪唾做 為腐餘抑刪,轴^具有剝除改良絲劑之能力及防止銅佈 線腐蝕之能力。 比較性例1 以相同於例1之方法實施測試,但其組成不含腐儀抑制劑& 疏基笨顿MBI))。測試結果顯示於下面的表2中,表2中之縮 寫字的意義如上面所定義。 [表2] 組成號 碼 胺之 種類 胺 (wt%)( 水 wt%) eg (wt %) THF NMP 剝除A1 Cu線之 A (5%) 線上改 腐餘 (wt% +EDG 良PR之 ) (48%) 能力 14 201224140The degree of corrosion; I 〇 · the same degree of corrosion as the control substrate; 〇: the same thickness as the control substrate, and negligible surface corrosion; △ • film thickness is smaller than the control substrate, and surface rot occurs And X: The copper wiring film is etched so that the film thickness is reduced by 1/2 or more. [Table 1] Amines of the composition number amine (wt%) Water (wt%) EG (wt%) THFA (wt%) NMP (5%) + EDG (48%) (wt%) Stripping the A1 line PR Corrosion on the capacity copper wire 1 MEA 7 20 20 53 ◎ ◎ 2 MEA 7 20 - 20 53 ◎ ◎ 3 MIPA 7 20 20 53 ◎ ◎ 4 MIPA 7 20 - 20 53 ◎ ◎ 5 DIPA 7 20 20 53 Δ ◎ 6 DIPA 7 20 - 20 53 Δ ◎ 7 TIPA 7 20 20 53 X ◎ 8 TIPA 7 20 - 20 53 X ◎ 9 2-MAE 7 20 - 20 53 ◎ ◎ 10 2-MAE 7 20 20 - 53 ◎ ◎ 12 201224140 11 MDEO A 7 20 20 - 53 X 12 MDEO A 7 20 20 53 X ◎ 13 DEEO A 7 20 20 53 X ◎ 14 DEEO A 7 20 - 20 53 X ◎ 15 AEEO A 7 20 20 - 53 Δ ◎ 16 AEEO A 7 20 - 20 53 Δ ◎ 17 3-APN 7 20 20 53 ◎ ◎ 18 3-APN 7 20 20 53 ◎ ◎ Note: MEA: monoethanolamine MIPA: monoisopropanolamine DIPA: diisopropanolamine TIPA: triisopropyl Alcoholamine AMP: 2-Alkyl-2-mercapto-1-propanol 2-MAE: 2-(decylamino)ethanol MDEOA: mercapto diethanolamine DEEOA: diethylethanolamine 13 201224140 AEEOA. Ethanolamine 3-APN: 3-Aminopropanolamine MDEA: Methyldiethanolamine MDMA: Mercapto Dimethanolamine EG Diethanol EDG: Diethylene glycol monoethyl ether NMP: N-decylpyrrolidine _ THFA: tetrahydrofurfuryl alcohol MBI: 2-mercaptobenazole As seen in Table 1 above, the composition of the present invention comprises 2-Siliconyl phenyl saliva is used as a rot residue, and the shaft has the ability to strip the modified silk agent and prevent corrosion of the copper wiring. Comparative Example 1 The test was carried out in the same manner as in Example 1, except that the composition did not contain a sulphur inhibitor & The test results are shown in Table 2 below, and the meaning of the indentation in Table 2 is as defined above. [Table 2] Amines of the composition number amine (wt%) (water wt%) eg (wt %) THF NMP Stripping A1 Cu line A (5%) Online refining residue (wt% + EDG good PR) (48%) Ability 14 201224140
(wt%) 1 MEA 7 20 20 53 ◎ X 2 MEA 7 20 - 20 53 ◎ X 3 MIPA 7 20 20 - 53 ◎ X 4 MIPA 7 20 - 20 53 ◎ X 5 DIPA 7 20 20 53 Δ Δ 6 DIPA 7 20 - 20 53 Δ Δ 7 TIPA 7 20 20 - 53 X ◎ 8 TIPA 7 20 - 20 53 X ◎ 9 AMP 7 20 20 53 ◎ X 10 AMP 7 20 20 53 ◎ X 11 2-MA 7 20 20 53 ◎ X E 12 2-MA 7 20 20 53 ◎ X E 13 MDE 7 20 20 - 53 X ◎ A 14 MDE 7 20 - 20 53 X ◎ A 15 MDM 7 20 20 53 X ◎ A 16 MDM 7 20 - 20 53 X ◎ A 15 201224140 --—^· 17 DEEO A 7 20 20 53 X △ DEEO A 7 20 20 53 X ◎ 19 AEEO A 7 --- ----- 20 20 - 53 Δ X 20 AEEO A 7 ~~·—— ------ 20 _ 20 53 Δ ◎ 21 3-AP N -- ---- 7 20 20 - 53 ◎ X 22 3-AP Si ---. · — 7 一 1 · 20 20 53 ◎ X: 面表2中所翻的,當含水的光關除組成含有初級醇 :ic:,Cu腐糊劑時,其剝除改良光阻劑之能力是不 好的’或疋’防止銅線_之能力顯著地下降。 例2 以相同於例i之方法實施測試,但&腐餘抑制劑 酒精之含量被改變,如下面表3之所示。測試 種類或是 表3中。 〇果頌不於下面之 [表3] 組成號 Cu腐 ME Wat eg THFA NMP Cu ik ^ ^ ^^5:注釋 16 201224140 碼 姓抑 制劑 A (wt %) er (wt %) (wt %) (wt%) (5%) +EDG (48%) (wt%) 之腐 4k 1 BIMD 7 20 20 - 53 A 沒有殘留的 腐触抑制劑 2 BIMD 7 20 - 20 53 A 沒有殘留的 腐姓抑制劑 3 IMD 7 20 20 53 A 沒有殘留的 腐姓抑制劑 4 IMD 7 20 20 53 A 沒有殘留的 腐#抑制劑 5 4-MI MD 7 20 20 53 A 沒有殘留的 腐#抑制劑 6 4-MI MD 7 20 _ 20 53 A 沒有殘留的 腐餘抑制劑 7 BTA 7 20 20 53 ◎ 殘留腐蝕抑 制劑 8 BTA 7 20 - 20 53 ◎ 殘留腐蝕抑 制劑 9 TTA 7 20 20 53 ◎ 殘留腐蝕抑 制劑 10 TTA 7 20 20 53 ◎ 殘留腐蝕抑 17 201224140 制劑 11 MBI 7 20 20 - 53 ◎ 沒有殘留的 腐蚀抑制劑 12 MBI 7 20 - 20 53 ◎ 沒有殘留的 腐蚀抑制劑 13 2,5-DT A 7 20 20 - 53 〇 沒有殘留的 腐蝕抑制劑 14 2,5-DT A 7 20 爭 20 53 〇 沒有殘留的 腐餘抑制劑 15 MBT 7 20 20 - 53 ◎ 沒有殘留的 腐钱抑制劑 16 MBT 7 20 - 20 53 ◎ 沒有殘留的 腐姓抑制劑 17 MBI 7 30 10 - 53 ◎ 沒有殘留的 腐餘抑制劑 18 MBI 7 30 10 53 ◎ 沒有殘留的 腐蚀抑制劑 註解: BIMD:苯基咪唑 IMD: 口米0坐 4-MIMD:4-曱基咪唑 BTA:苯基三唑 TTA:四〇坐 201224140 MBI:2-巯基苯咪唑 2,5-DTA: 2,5-二疏基_ι,3,4_η塞二唆 MBT: 2-疏基苯基H塞唾 做腐irtr表3之結果所看刺,當不含縣群之化合物被用 ::抑制劑時,佈線被雜’或是腐飿抑制劑殘留下來,但當 舰抑糊朗含蝴t合物讀基群,像2·絲紗坐、2,5_ 入气土 ’,4嚷一嗤、或2_疏基苯基麵等時,線之腐姓實質上完 王被防止,且沒有腐蝕抑制劑殘留下來。 [例3] 户以相同於例1之方法實施測試,但使用具空間位阻的amp(2_ 乱基-2-曱基小丙醇)做為初級胺。測試結果顯示於下面的表4中。(wt%) 1 MEA 7 20 20 53 ◎ X 2 MEA 7 20 - 20 53 ◎ X 3 MIPA 7 20 20 - 53 ◎ X 4 MIPA 7 20 - 20 53 ◎ X 5 DIPA 7 20 20 53 Δ Δ 6 DIPA 7 20 - 20 53 Δ Δ 7 TIPA 7 20 20 - 53 X ◎ 8 TIPA 7 20 - 20 53 X ◎ 9 AMP 7 20 20 53 ◎ X 10 AMP 7 20 20 53 ◎ X 11 2-MA 7 20 20 53 ◎ XE 12 2-MA 7 20 20 53 ◎ XE 13 MDE 7 20 20 - 53 X ◎ A 14 MDE 7 20 - 20 53 X ◎ A 15 MDM 7 20 20 53 X ◎ A 16 MDM 7 20 - 20 53 X ◎ A 15 201224140 --—^· 17 DEEO A 7 20 20 53 X △ DEEO A 7 20 20 53 X ◎ 19 AEEO A 7 --- ----- 20 20 - 53 Δ X 20 AEEO A 7 ~~·—— ------ 20 _ 20 53 Δ ◎ 21 3-AP N -- ---- 7 20 20 - 53 ◎ X 22 3-AP Si ---. · — 7 一 1 · 20 20 53 ◎ X : Turned in Table 2, when the water-containing light is turned off to contain the primary alcohol: ic:, Cu paste, its ability to strip the improved photoresist is not good 'or 疋' to prevent copper wire _ The ability has dropped significantly. Example 2 The test was carried out in the same manner as in Example i, except that the <preservative inhibitor alcohol content was changed as shown in Table 3 below. The type of test is either in Table 3. The results are not as follows [Table 3] Composition number Cu rot ME Wat eg THFA NMP Cu ik ^ ^ ^^5: Note 16 201224140 Codename inhibitor A (wt %) er (wt %) (wt %) ( Wt%) (5%) +EDG (48%) (wt%) Corrosion 4k 1 BIMD 7 20 20 - 53 A No residual corrosion inhibitor 2 BIMD 7 20 - 20 53 A No residual rot inhibitor 3 IMD 7 20 20 53 A No residual rot inhibitor 4 IMD 7 20 20 53 A No residual rot #Inhibitor 5 4-MI MD 7 20 20 53 A No residual rot #Inhibitor 6 4-MI MD 7 20 _ 20 53 A No residual corrosion inhibitor 7 BTA 7 20 20 53 ◎ Residual corrosion inhibitor 8 BTA 7 20 - 20 53 ◎ Residual corrosion inhibitor 9 TTA 7 20 20 53 ◎ Residual corrosion inhibitor 10 TTA 7 20 20 53 ◎ Residual corrosion suppression 17 201224140 Preparation 11 MBI 7 20 20 - 53 ◎ No residual corrosion inhibitor 12 MBI 7 20 - 20 53 ◎ No residual corrosion inhibitor 13 2,5-DT A 7 20 20 - 53 〇 no residual corrosion inhibitor 14 2,5-DT A 7 20 contend 20 53 〇 no residual residual inhibitor 15 MBT 7 20 20 - 53 ◎ no residual rot Inhibitor 16 MBT 7 20 - 20 53 ◎ No residual septic inhibitor 17 MBI 7 30 10 - 53 ◎ No residual residual inhibitor 18 MBI 7 30 10 53 ◎ No residual corrosion inhibitor Notes: BIMD: Benzene Imidazole IMD: mouth rice 0 sitting 4-MIMD: 4-mercaptoimidazole BTA: phenyl triazole TTA: four squats 201224140 MBI: 2-mercaptobenzazole 2,5-DTA: 2,5-diyl ι,3,4_η塞唆唆 MBT: 2-carbyl phenyl H-salted rot irtr Table 3 results are seen as thorns, when the compound containing no group is used:: inhibitor, the wiring is mixed' or It is a rot inhibitor that remains, but when the ship suppresses the scent of the compound, it is like 2, silk yarn sitting, 2,5_ into the gas soil, 4 嚷 嗤, or 2 疏 phenyl When the surface is equal, the rot of the line is essentially prevented, and no corrosion inhibitor remains. [Example 3] The test was carried out in the same manner as in Example 1, except that sterically hindered amp (2_ranyl-2-mercaptopropanol) was used as the primary amine. The test results are shown in Table 4 below.
19 20122414019 201224140
如由上面表4中之絲所看到的,不僅在水與腐崎制劑被 添加到現成之情況’而且在金;|腐财使用於只含酒精而不 含水之有敝賴航下,AMP財效地能社A1與Cu線的腐 姓’同時也能完全地剝除改良的光阻劑。 由上面測試結果可以看&,在製備含水的光關除組成時, 若使用強雖減乙醇胺或含錄化合物之雜群#做雜抑制 劑,則可以完全地剝除嚴重改良的光阻劑,同時也可以防止銅線的 腐蝕。而且,當具空間阻位的初級醇胺(AMp)使用於有機的不含水 的剝除組成時,縱使沒有腐蝕抑制劑,銅線也不會被腐蝕。 雖然本發明已經以示例性實施例加以說明,但應了解到,在 不違背本發明之精神與範疇下,與本技藝相關之專業人士可對實 施例做各種不同的改變,以及,以等效物來取代相關元件。此外, 亦可做許多修正來適應特別之情況,或是以材料來符合本發明之 教旨,它們均不違反本發明之精神與範疇。因此,在此要特別強 調,本發明不被限制於用來說明本發明之實施方法的實施例子。 201224140 【圖式簡單說明】 圖1是A1佈線膜在玻璃基板上的顯微照片,其中,光阻劑尚 未被去除,且其已在溫度17〇它之爐中被熱處理1〇分鐘。 圖2是一顯微照片,顯示殘留在基板上未被去除的改良的光 阻劑’其係將基板(在170。(:熱處理1〇分鐘後)浸入5〇 X:之剝除 組成30秒後之結果,用來評估光阻劑去除之程度(被評估為“X”)。 圖3是一顯微照片’顯示殘留在基板上未被去除的改良的光 阻劑的一部分’其係將基板(在17〇它熱處理1〇分鐘後)浸入5〇 t 之剝除喊3G秒後之絲,峰評估絲縣除之程度(被評估為 圖4是一顯微照片,顯示改良的光阻劑已完全由基板上去除, ”係將基板(在17。。°_理1。分鐘麟人5。。。之剝除組成3。 秒後之結果’絲評估光賴去除之减(被評估為“◎,,)。 圖5是Cu佈線膜在基板上的SEM顯微照片,其上之 尚未被去除。 圖6是SEM照片’顯示將Cu玻璃基板(其上之光阻劑尚 去除)浸入5〇 °C之剝除組成1〇分鐘後之結果,用來 腐餘之程度,其被聰為“◎”。 表面 顯示將Cu玻璃基板(其上之光阻劑尚未被 °C之剝除組成10分鐘後之結果’用來評估 圖7是SEM照片, 去除)浸入50 °C之系丨財 腐麵之程度’其被評估為“〇,,。 圖8是SEM照片,As seen from the silk in Table 4 above, not only in the case where water and sakizaki preparations are added to the ready-made situation, but also in gold; | rot is used in alcohol-only and water-free, AMP The stagnation of the A1 and Cu lines of the financial efficiency can also completely remove the improved photoresist. From the above test results can be seen &, in the preparation of aqueous light off the composition, if the use of strong ethanolamine or mixed compound miscellaneous group # as a hetero-inhibitor, you can completely remove the severely improved photoresist It also prevents corrosion of copper wires. Moreover, when the sterically hindered primary alkanolamine (AMp) is used in an organic, non-aqueous stripping composition, the copper wire is not corroded even without a corrosion inhibitor. Although the present invention has been described in terms of exemplary embodiments, it will be understood that those skilled in the art can make various changes in the embodiments and equivalents without departing from the spirit and scope of the invention. Replace the relevant components. In addition, many modifications may be made to adapt a particular situation, or the material is intended to be in accordance with the teachings of the invention, without departing from the spirit and scope of the invention. Therefore, it is to be emphasized that the invention is not limited to the embodiment of the embodiment of the invention. 201224140 [Simple description of the drawing] Fig. 1 is a photomicrograph of the A1 wiring film on a glass substrate in which the photoresist has not been removed, and it has been heat-treated at a temperature of 17 Torr for 1 minute. Figure 2 is a photomicrograph showing a modified photoresist that has not been removed on the substrate. It is a substrate (at 170 ° (after heat treatment for 1 minute) immersed in 5 〇 X: stripping composition for 30 seconds The result was used to evaluate the extent of photoresist removal (evaluated as "X"). Figure 3 is a photomicrograph 'showing a portion of the improved photoresist that was not removed on the substrate' The substrate (after 17 热处理 heat treatment for 1 〇) was immersed in 5 〇t stripped and shredded for 3G seconds, and the peak was evaluated by the degree of silk count (as evaluated as Figure 4 is a photomicrograph showing improved photoresist The agent has been completely removed from the substrate, "the system will be the substrate (at 17 ° ° ° 1 1. Min Lin 5 5 .. stripping composition 3. After 2 seconds of the results of the silk evaluation of the light removal removal (evaluated Fig. 5 is an SEM micrograph of a Cu wiring film on a substrate, which has not been removed. Fig. 6 is an SEM photograph 'showing a Cu glass substrate (on which the photoresist is removed) The result of immersion in 5 〇 ° C for 1 〇 minutes, used to the extent of the rot, it was sung as " ◎". The board (the result of which the photoresist was not removed by °C for 10 minutes) was used to evaluate the degree of immersion in the 50 °C 丨 腐 腐 ' ' ' ' 50 50 50 50 50 50 "Hey,,. Figure 8 is a SEM photograph,
Cu表面Cu surface
除)浸入50 °C之剝除組成1〇分鐘後之結果,用來評估 麵之知度,其被評估為“ △”。 21 201224140 圖9是SEM照片,顯示將Cu玻璃基板(其上之光阻劑尚未被 去除)浸入50 °C之剝除組成10分鐘後之結果,用來評估Cu表面 腐蝕之程度,其被評估為“X”。 【主要元件符號說明】 22The results of the immersion at 50 °C for 1 minute were used to evaluate the surface, which was evaluated as "△". 21 201224140 Figure 9 is a SEM photograph showing the results of immersing a Cu glass substrate (on which the photoresist has not been removed) at 50 ° C for 10 minutes to evaluate the degree of corrosion on the Cu surface, which was evaluated. Is "X". [Main component symbol description] 22