201116946 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種適於清洗多金 利用水進行沖洗步驟時不會發生任 隨後 ::之微電子光阻清洗組合物。本發明亦係: 电月組合物清洗該等多金屬微電子裝置之方法。 【先前技術】 ° ^嘗試使用多種目前可取得的鹼基光阻清洗組合物清洗 夕金屬（如，Al/Mo或AI/Ti)微電子穿f 主 良好,。然而，當隨後利用習知的水清洗步驟去除裝置表面 之清洗組合物時，使與該微電 、、 .s „ 发置上之多金屬堆接觸後 通㊉為pH 9或更高之鹼性水溶液 之間形成一產生及加速電化學（電. 5夕種不同金屬 電化于(電流)腐蝕的電流電流。因 …有一如利用習知溶劑，通常為異丙醇之「中間 沖洗步驟。這中間沖洗步驟係有助於自該微電子裝置料 清洗組合物中之鹼性化合物， ’、 m ^ …、设在水冲洗時再使該微電 :裝置與水接觸。這中間沖洗步驟只是應省略的另一額外 衣程步驟。此外’需要提供一種用於多金屬微電子裝置之 產生良好清洗效果同時保護該金屬免於電流腐银之良好清 洗組合物。 【發明内容】 一根據本發明，提供—種用於清洗多金屬微電子裝置之 半-水性、鹼性清洗組合物’該組合物係由以下組成： 0)約10%至約35%之水； 144690.doc 201116946 (b) 約5%至約1 5%之至少一種烷醇胺； (c) 約1〇〇/0至約50%之選自由N-甲基咣咯啶酮或冰曱基 吡咯啶酮與環丁颯之混合物組成之群之溶劑； (d) 約2 %至約1 〇%之葡萄糖酸或藉由水中水解產生葡萄 糖酸之化合物； (e) 約1¾至約8%之至少一種如式HO(CH2CH2〇)nCH2CH2〇H 之寡乙二醇，其中η為I或更大；及 (f) 視情況選用之約10%至約40%之至少一種二乙二醇單 炫基醚’其中該烧基含有1至4個碳原子； 其中該等百分比為基於該組合物總重量之重量百分比且當 烷醇胺之百分比等於或小於6%時，队曱基吡咯啶酮溶^ 在組合物中之量為20%或更多，及當烧醇胺之百分比為9% 或更多時，N-曱基吡咯啶酮溶劑的量可等於或小於2〇%。 本發明清洗組合物對於清洗多金屬微電子裝置及抑制微電 子裝置中金屬的電流腐姓係特別有用的。 5—溫度下用於清洗該微電子裝置而在= 中不發生任何顯著或實質之金屬電流腐蝕。 【實施方式】 本發明之半-水性、鹼性清洗組合物將具有約1〇重量％至 約35重量％之水存在於該組合物中。該水可為水本身或作 為該組合物之另-組分之水溶液的—部分的水，或源自兩 種來源之混合物。該組合物中水量較佳為約Η重量％至約 3 0重量。/。，更佳為約丨5曹哥 々川室里/〇至約30重量％，再更佳為約 1 8重量％至約25重量％。 144690.doc 201116946 山該至少一種院醇胺可係任何適宜的燒醇胺，包括】至6個 奴原子，較佳為1至4個碳原子，更佳為〗至3個碳原子之烷 酉子胺。尤佳者為單異丙醇胺及二乙醇胺。該組合物中烧醇 胺組分之存在量可為約5%至約15%，較佳為⑽至約 1 〇% ’更佳為約6%至約8% ’及再更佳為6%至7%。 用於本發明清洗組合物之溶劑為Μ·甲基吡咯啶酮或甲 基比11各咬酮與壤丁礙之混合物。該⑷溶劑將&約至約 〇裒丁砜及約1 〇%至約3 〇% Ν_甲基吡咯啶酮之量存在於 該組合物中。該溶劑之總量將為約1〇%至約5〇%，較佳為 約20%至約50%，更佳為約3〇%至約5〇%及再更佳為約鳩 至約40%。在本發明組合物中，當烧醇胺之百分比等於或 小於6%時’ Ν.甲基。比略㈣溶劑在該組合物中的量為鳩 或更多，及當烷醇胺之百分比為9%或更多時，ν_甲基吡 洛咬g同的量可等於或小於2〇%。 土 葡萄糖酸或纟中水解後產生葡萄糖酸之化合物係用作組 合物之電流腐蝕抑制劑組分。當使用葡萄糖酸時，通常以 50%水溶液形式使用，該5〇%水係組合物中所容許之總水 I之邠刀。作為水解產生葡萄糖酸之化合物實例，可提 及葡萄糖酸δ-内醋。在該組合物中作為葡萄糖酸之葡萄糖 酸的總量可為約2%至約io%’較佳為約2%至約6%，更佳 為約3%至約6%及最佳為約3%。因此，當該組合物中需具有 如3%葡萄糖酸時，則使用6%之5〇%的葡萄糖酸水溶液。 在本發明清洗組合物中，儘管已發現葡萄糖酸係一有效 的電流腐触抑制劑’然已發現葡萄糖酸與該組合物中所用 144690.doc 201116946 ▲之有機溶劑不高度互溶。製備本發明清洗組合物時，在該 5周配物中有充足的水，該互溶 卜力乂问題。然而，在使用 該清洗組合物期間，特別當該清洗是在約贼至約_之 高度理想的溫度下進行時水蒸發，已發現出現相分離且該 清洗組合物變渾濁。為克服關題及㈣，已發現該組合 物必須有至少一種式HO(CH2CH2〇)nCH2C職之寡乙二醇也分 (其中η為1或更大’較佳為1至4)存在於本發明清洗組合物 中。此組分之存在性抑制或防止相分離的發生且使本發明 清，組合物能保持該葡萄糖酸組分之電流腐蚀抑制性能。 該募乙二醇組分較佳為二乙二醇、三乙二醇及四乙二醇。 驚人的是，該等寡乙二醇組分能抑制或防止上述相分離及 減少本發明組合物中電流腐蝕之抑制，因為乙二醇或丙三 醇不具有抑制或防止上述相分離及減少本發明組合物中電 流腐蝕之抑制的能力。該至少一種募乙二醇將以約以至 約8%，較佳為約2%至約6%，更佳為約3%至約5%，及再 更佳為約5%之量存在於該組合物中。 本發明清洗組合物視情況在該組合物中將有至少―種二 乙一醇單烧基胺存在，其中該烧基含有1至4個碳原+。若 至少一種二乙二醇單烷基胺組分存在於本發明組合物中， 較佳S亥組分係存在的，其將以約1 〇%至約4〇%，較佳為約 10%至約30%，更佳為約2〇%至約3〇%，及再更佳為約25% 至約28%之量存在。 本發明組合物可用於任何足以清洗光阻之多金屬微電子 裝置及其他殘留物，諸如電漿及蝕刻殘留物的適宜清洗溫 144690.doc 201116946 度及時間下，但特定言之能在約5〇。(：至約6〇°C之溫度下清 洗该等多金屬裝置約30至約6〇秒的時間及由此甚至使該清 洗過的裝置接受隨後水性沖洗時亦能同時抑制該裝置之金 屬的電流腐飯。 ’ 下列表1描述本發明清洗組合物之實例。表1及下列表2 係使用下列縮寫。該等百分比係重量百分比。 MIPA=單異丙醇胺 DEA=二乙醇胺 GLU=葡萄糖酸-5〇%水溶液 5-LAC=葡萄糖酸δ_内酯 SFL =環丁碾 NMP=N-甲基。比σ各啶酮 DEG=二乙二醇 EG=乙二醇 TEG=四乙二醇 CAR=卡必醇（二乙二醇單甲基醚） GLY=丙三醇201116946 VI. Description of the Invention: [Technical Field] The present invention relates to a microelectronic photoresist cleaning composition which is suitable for cleaning a multi-gold rinsing step using water. The invention is also a method of cleaning the multi-metal microelectronic devices by the electro-month composition. [Prior Art] ° ^Try to use a variety of currently available base photoresist cleaning compositions to clean the metal (eg, Al/Mo or AI/Ti) microelectronics. However, when the cleaning composition on the surface of the device is subsequently removed by a conventional water washing step, the alkaline electrode stack is placed in contact with the multi-metal stack on the micro-electric, .s „ A current and a current between the aqueous solution is generated and accelerated (the current is different from the (metal) corrosion of the different metals. Because of the use of a conventional solvent, usually the intermediate rinse step of isopropanol. The rinsing step is to facilitate the cleaning of the alkaline compound from the composition of the microelectronic device, ', m ^ ..., which is set to be in contact with water when the water is rinsed. The intermediate rinsing step should only be omitted. Another additional process step. In addition, it is desirable to provide a good cleaning composition for a multi-metal microelectronic device that produces a good cleaning effect while protecting the metal from current rot silver. [Invention] According to the present invention, A semi-aqueous, alkaline cleaning composition for cleaning a multi-metal microelectronic device. The composition consists of: 0) from about 10% to about 35% water; 144690.doc 201116946 (b) about 5 % About 1 5% of at least one alkanolamine; (c) from about 1 〇〇/0 to about 50% selected from the group consisting of N-methylpyrrolidone or a mixture of haloperidone and cyclobutyl hydrazine a solvent of the group; (d) from about 2% to about 1% gluconic acid or a compound which produces gluconic acid by hydrolysis in water; (e) at least one of from about 13⁄4 to about 8%, such as the formula HO(CH2CH2〇)nCH2CH2〇 H oligoethylene glycol, wherein η is I or greater; and (f) optionally from about 10% to about 40% of at least one diethylene glycol monoethyl ether, wherein the alkyl group contains from 1 to 4 a carbon atom; wherein the percentage is based on the weight percent of the total weight of the composition and when the percentage of the alkanolamine is equal to or less than 6%, the amount of the thiopyrrolidone dissolved in the composition is 20% or Further, and when the percentage of the alkanolamine is 9% or more, the amount of the N-decylpyrrolidone solvent may be equal to or less than 2%. The cleaning composition of the present invention is for cleaning a multi-metal microelectronic device and suppressing The current rot of metal in a microelectronic device is particularly useful. 5 - used to clean the microelectronic device at temperature without any significant or substantial occurrence in = Metal Current Corrosion. [Embodiment] The semi-aqueous, alkaline cleaning composition of the present invention will have from about 1% by weight to about 35% by weight water present in the composition. The water may be water itself or as A portion of the aqueous solution of the other component of the composition, or a mixture of the two sources. The amount of water in the composition is preferably from about 3% by weight to about 30% by weight. More preferably, it is about 丨. 5 Cao Ge Chuanchuan room / 〇 to about 30% by weight, and even more preferably from about 18% by weight to about 25% by weight. 144690.doc 201116946 The at least one alkoxide can be any suitable alkanolamine, Including: to 6 slave atoms, preferably 1 to 4 carbon atoms, more preferably an alkane sulfonamide of up to 3 carbon atoms. Particularly preferred are monoisopropanolamine and diethanolamine. The alkanolamine component of the composition may be present in an amount of from about 5% to about 15%, preferably from (10) to about 1% by weight, more preferably from about 6% to about 8%, and even more preferably 6%. To 7%. The solvent used in the cleaning composition of the present invention is Μ·methylpyrrolidone or a mixture of methyl ketones and ketones. The (4) solvent is present in the composition in an amount of from about 1 to about sulfolane and from about 1% to about 3 % Ν-methylpyrrolidone. The total amount of the solvent will be from about 1% to about 5%, preferably from about 20% to about 50%, more preferably from about 3% to about 5%, and still more preferably from about 5% to about 40%. %. In the composition of the present invention, when the percentage of the alkanolamine is equal to or less than 6%, the Ν.methyl group. The amount of the solvent in the composition is 鸠 or more, and when the percentage of the alkanolamine is 9% or more, the amount of ν-methylpirobitone may be equal to or less than 2%. . A compound which produces gluconic acid after hydrolysis of gluconic acid or hydrazine is used as a component of the current corrosion inhibitor of the composition. When gluconic acid is used, it is usually used in the form of a 50% aqueous solution, which is the total water I allowed in the 5% aqueous composition. As an example of a compound which hydrolyzes gluconic acid, gluconic acid δ-endo vinegar can be mentioned. The total amount of gluconic acid as gluconic acid in the composition may range from about 2% to about io%', preferably from about 2% to about 6%, more preferably from about 3% to about 6%, and most preferably from about 6% to about 6%. 3%. Therefore, when it is necessary to have, for example, 3% gluconic acid in the composition, 6% of a 5 % by weight aqueous solution of gluconic acid is used. In the cleaning compositions of the present invention, gluconic acid has been found to be an effective current rotatory inhibitor. It has been found that gluconic acid is not highly miscible with the organic solvent used in the composition of 144690.doc 201116946 ▲. In preparing the cleaning composition of the present invention, there is sufficient water in the 5 week formulation, which is a problem of mutual dissolution. However, during the use of the cleaning composition, particularly when the cleaning is carried out at a temperature as high as about a thief to a high temperature, it has been found that phase separation occurs and the cleaning composition becomes cloudy. In order to overcome the problem and (4), it has been found that the composition must have at least one oligoethylene glycol of the formula HO(CH2CH2〇)nCH2C, which is also present (where η is 1 or greater 'preferably 1 to 4) is present in the present Inventive cleaning compositions. The presence of this component inhibits or prevents the occurrence of phase separation and allows the present invention to maintain the current corrosion inhibiting properties of the gluconic acid component. The ethylene glycol component is preferably diethylene glycol, triethylene glycol and tetraethylene glycol. Surprisingly, the oligoethylene glycol components inhibit or prevent the above phase separation and reduce the inhibition of galvanic corrosion in the compositions of the present invention because ethylene glycol or glycerol does not inhibit or prevent the above phase separation and reduce the present The ability of the invention to inhibit the suppression of galvanic corrosion. The at least one ethylene glycol will be present in an amount of from about 8%, preferably from about 2% to about 6%, more preferably from about 3% to about 5%, and still more preferably about 5%. In the composition. The cleaning compositions of the present invention will optionally have at least one of the ethylene glycol monoalkylamines present in the composition, wherein the alkyl groups contain from 1 to 4 carbon atoms. If at least one diethylene glycol monoalkylamine component is present in the compositions of the invention, preferably a S-component is present, which will range from about 1% to about 4%, preferably about 10%. It is present in an amount of from about 25%, more preferably from about 2% to about 3%, and still more preferably from about 25% to about 28%. The composition of the present invention can be used in any multi-metal microelectronic device and other residues sufficient to clean photoresist, such as plasma and etching residues, at a suitable cleaning temperature of 144690.doc 201116946 degrees and time, but in particular, at about 5 Hey. (: cleaning the multi-metal devices at a temperature of about 6 ° C for a period of about 30 to about 6 seconds and thereby even inhibiting the metal of the device when the washed device is subjected to subsequent aqueous washing Current saute. 'Examples of cleaning compositions of the present invention are described in Table 1. The following abbreviations are used in Table 1 and Table 2 below. The percentages are percentages by weight. MIPA = monoisopropanolamine DEA = diethanolamine GLU = gluconic acid -5〇% aqueous solution 5-LAC=gluconic acid δ_lactone SFL=cyclobutine NMP=N-methyl. Ratio σ each ketone DEG=diethylene glycol EG=ethylene glycol TEG=tetraethylene glycol CAR = carbitol (diethylene glycol monomethyl ether) GLY = glycerol
144690.doc 201116946 為評估上述組合物八至1，使用具有Al/Ti雙金屬線之TFT 玻璃微電子基板。該等基板係在約50°C至約601：下該清洗 冷液中處理約3〇至約6〇秒的時間。隨後將該等清洗過的基 板浸入55清洗溶液（95%水）中達1至3分鐘（以模仿無任何中 間沖洗之水沖洗環境）並隨後評估任何電流腐蝕之等級。 斤有上述、.且合物A至I均徹底洗淨該基板而無任何顯而易見 的電流腐蝕發生且無渾濁形成。 為達比較之目的，調配下列表2中之對照組合物人八至ee 且接受相同測試條件。 1—-------— _ 表2 __組合物 AA BB CC DD EE __^ ΜΙΡΑ Ct?T 25 '6 6 25 6 25 6 25 ~ 6 orL, NMP ~~ΤϊτΤτ~~ 10 20 10 20 10 20 10 15 10 15 yj-LlJ .___TEG 6 6 6 6 6 1 5 EG 5 _ GLY 5 ---—-— 1_ CAR ~ 28 28 28 37 33 無葡萄糖酸之組合物AA具有顯著的電流腐蝕。組合物 BB與CC除了利用乙二醇及丙三醇取代四乙二醇之外皆與 發明組合物A與B相同。該等對照組合物BB與CC出現不希 望的渾濁且該葡萄糖酸經歷相分離。對照組合物DD與EE 均形成顯而易見的渾濁而導致相分離。在該等對照組合物 中’低（6%)MIPA與低（15%)ΝΜΡ之組合產生此等結果，而 類似本發明之組合物’其中烷醇胺（ΜΙΡΑ)之百分比等於或 144690.doc 201116946 小於6%且組合物中NMP溶劑的量為20〇/〇或更多，或當炫醇 胺（MIPA)之百分比為9%或更多時’ NMP的量為等於或小 於20% ’則此渾濁及相分離皆無發生。因此在本發明組合 物中’無論MIPA或NMP溶劑皆必須處於其高濃度範圍 内’意即當烷醇胺之百分比等於或小於6%時，組合物十 N-甲基吡咯啶酮溶劑的量為2〇%或更多，及當烷醇胺之百 分比為9%或更多時，N-曱基吡咯啶酮的量可等於 J、於 儘管已藉參考本發明料實施例而將本發明描述於本女144690.doc 201116946 To evaluate the above compositions 8 to 1, a TFT glass microelectronic substrate having an Al/Ti bimetallic wire was used. The substrates are treated in the rinse liquid at a temperature of from about 50 ° C to about 601 : for a period of from about 3 Torr to about 6 Torr. The washed substrates were then immersed in 55 wash solutions (95% water) for 1 to 3 minutes (to mimic the water rinse environment without any intermediate rinse) and then evaluated for any level of galvanic corrosion. The above-mentioned, and the compounds A to I completely washed the substrate without any obvious galvanic corrosion and no turbidity formation. For comparison purposes, the control group persons in Table 2 below were conditioned to the same test conditions. 1—-------— _ Table 2 __Composition AA BB CC DD EE __^ ΜΙΡΑ Ct?T 25 '6 6 25 6 25 6 25 ~ 6 orL, NMP ~~ΤϊτΤτ~~ 10 20 10 20 10 20 10 15 10 15 yj-LlJ .___TEG 6 6 6 6 6 1 5 EG 5 _ GLY 5 ------ 1_ CAR ~ 28 28 28 37 33 The gluconic acid-free composition AA has significant galvanic corrosion . The compositions BB and CC were identical to the inventive compositions A and B except that ethylene glycol and glycerol were used in place of tetraethylene glycol. The control compositions BB and CC showed undesirable turbidity and the gluconic acid undergoes phase separation. Both the control compositions DD and EE formed an apparent turbidity resulting in phase separation. The combination of 'low (6%) MIPA and low (15%) hydrazine in these control compositions produced these results, while compositions similar to the invention 'where the percentage of alkanolamine (ΜΙΡΑ) is equal to or 144690.doc 201116946 is less than 6% and the amount of NMP solvent in the composition is 20 〇 / 〇 or more, or when the percentage of stanolamine (MIPA) is 9% or more, the amount of 'NMP is equal to or less than 20%' This turbidity and phase separation did not occur. Thus, in the composition of the present invention, 'whether the MIPA or NMP solvent must be in its high concentration range' means that the amount of the composition of the ten N-methylpyrrolidone solvent is equal to or less than 6%. 2% or more, and when the percentage of alkanolamine is 9% or more, the amount of N-decylpyrrolidone may be equal to J, although the invention has been described with reference to the embodiments of the present invention. Described in this woman
中，但應瞭解在不 範圍相背離下，可 所有落在附屬申請 改良及變動。 144690.docHowever, it should be understood that in the absence of scope, all of the improvements and changes in the sub-applications may be made. 144690.doc