TW201207100A - Cleaning composition, cleaning method using the same and fabricating method of semiconductor device - Google Patents
Cleaning composition, cleaning method using the same and fabricating method of semiconductor device Download PDFInfo
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- TW201207100A TW201207100A TW100126795A TW100126795A TW201207100A TW 201207100 A TW201207100 A TW 201207100A TW 100126795 A TW100126795 A TW 100126795A TW 100126795 A TW100126795 A TW 100126795A TW 201207100 A TW201207100 A TW 201207100A
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201207100 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種清潔組成物、使用其的洗淨方法 及半導體元件的製造方法。 【先前技術】 於積體電路之製造中，正型光阻劑被用作中間遮罩。 具體而言，於一系列之光蝕刻與電漿蝕刻組合而成的加工 步驟中，於半導體基板（晶圓基板）上，被用作用以移動 光罩之光罩圖案的介質。該圖案化之光阻劑薄膜 (photoresist film)可於積體電路之製造步驟之規定階段自 基板上除去。通常情況下，該光阻劑薄膜之除去可藉由以 下2種方法而進行。 第1方法是包含使被光阻劑包覆之基板首先與由有 溶劑與胺所構成之細劑之剝離劑溶液接綱「濕式剝 步驟」的方法。然而，於該使用剝離劑溶液之方法中， 在製造中對光阻_騎行紫外_射或錢處理之情 時，存在無法將該光阻劑薄膜完全除去之現象。作為其 要原因，可列舉：於光阻劑薄膜中，由於如上所述之^ 線照射處理等而變質，變得難以轉於_劑溶液中。 且’於此種濕式剝離法中所使用之溶劑，在多數情況下 氣體的讎刻中所形成之無機殘 第2方法可列舉㈣灰化。於該方法中，首先 半導體基板之表面使抗侧薄膜燃燒，使塗佈有光随 4 201207100. 之曰a圓暴露於以氧為基質之電敷中。該處理於真空室内進 行，因此難以受到空氣中之微粒子或金屬之污染之影響。 基於§亥優點，於積體電路之製造步驟中廣泛利用上述電漿 灰化。 然而，於將上述之電漿蝕刻之副產物除去之方面而 吕，電漿灰化並不能說完全有效。因此，即使藉由電漿灰 化、上述之濕式剝離，電漿蝕刻副產物（殘渣）之除去亦 存在藉由洗淨溶液等而另外洗淨除去之必要。而且，於電 漿灰化中，亦存在將由此而產生之副產物（殘渣）一併洗 淨除去之必要。 現在可以獲得數種市售品（例如EKC Tedm〇1〇gy Inc 么司製造之EKC 265 (商品名）、Ashland Chemical公司製 ie之 ACT 935 (商品名）、Mitsubishi Gas Chemical 公司製 造之ELM C-30 (商品名）），用以除去電漿灰化後之由於 電襞餘刻而殘存之電漿蝕刻副產物（殘渣）。關於該些產 品’亦作為專利文獻而被公開（參照專利文獻！〜專利文 獻3、專利文獻4)。然而，該些市售產品之PH高達11以 上或包含氟化合物，雖然可有效地分解電漿蝕刻殘渣，但 存在亦侵襲基板上之金屬或氧化物之蒸鍍圖案之現象。雖 然於該些產品中適用有腐蝕抑制劑，但僅僅由此難以獲得 • 充分之腐蝕防止性。 對此’開發了並不對半導體基板造成有害影響之清潔 組成物（參照專利文獻5〜專利文獻7)。其是水系之組成 物C清潔液），含有羥胺化合物、鹼性化合物、有機酸等酸， 201207100 由此可-面維持洗淨性，-面達成腐餘防止。而且，該清 潔液是以水為主介質之水系清潔液，相對於有機系清潔液 而言為低成本，且具有環境適應性優異之 [先前技術文獻] ” [專利文獻] [專利文獻1]美國專利第5279771號說明書 [專利文獻2]美國專利第5419779號說明書 [專利文獻3]美國專利第563〇9〇4號說明書 [專利文獻4]日本專利3891768號說明書曰 [專利文獻5]日本專利第3871257號公報 [專利文獻6]日本專利第3513491號公報 [專利文獻7]日本專利第414732〇號公報 【發明内容】 ，由上述專利文獻5〜專利文獻7中揭示之新技術， Y使半導體基板之清潔组成物中的金屬舰防止性飛躍性 ，高。然而，本發明者等人為了達成更高之性能而繼續研 九開發。特別是推進如下之清潔組成物之探索：所述清潔 組成物於特定之清潔劑顯示出高的洗淨力之實質上為中性 之區域中，不僅發揮金屬之高的腐蝕防止性，而且亦進一 步發揮矽的高的腐蝕防止性。 <本發明之目的在於提供一種清潔組成物、使用其的洗 =法及半導體元件的製造方法，所述清潔組成物可解決 =質上被調整為中性的含有特定清雜之清雜成物中 特有的問題，可防止半導縣板之金屬相狀的由於 6 201207100201207100 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a cleaning composition, a cleaning method using the same, and a method of manufacturing a semiconductor device. [Prior Art] In the manufacture of an integrated circuit, a positive photoresist is used as an intermediate mask. Specifically, in a series of photolithography and plasma etching processes, a semiconductor substrate (wafer substrate) is used as a medium for moving the mask pattern of the photomask. The patterned photoresist film can be removed from the substrate at a specified stage of the manufacturing process of the integrated circuit. In general, the removal of the photoresist film can be carried out by the following two methods. The first method is a method comprising a step of "wet stripping" a substrate coated with a photoresist first with a stripper solution containing a fine agent composed of a solvent and an amine. However, in the method of using the stripper solution, there is a phenomenon that the photoresist film cannot be completely removed when the photoresist is subjected to ultraviolet light irradiation or money treatment in the production. The reason for this is that, in the photoresist film, it is deteriorated by the above-described irradiation treatment or the like, and it becomes difficult to transfer it to the solution. Further, the solvent used in such a wet stripping method is, in many cases, an inorganic residue formed in the etching of a gas. (A) ashing is exemplified. In this method, first, the anti-side film is burned on the surface of the semiconductor substrate, and the coated light is exposed to an oxygen-based electric charge with a circle of 2012a. This treatment is carried out in a vacuum chamber, and thus is hardly affected by the contamination of particles or metals in the air. Based on the advantages of § hai, the above-mentioned plasma ashing is widely utilized in the manufacturing steps of integrated circuits. However, in terms of removing the above-mentioned plasma-etched by-products, plasma ashing cannot be said to be completely effective. Therefore, even if the plasma ashing or the above-described wet detachment is performed, the removal of the plasma etching by-product (residue) is additionally required to be washed and removed by washing the solution or the like. Further, in the plasma ashing, it is also necessary to wash and remove the by-products (residues) thus produced. Several commercial products are now available (for example, EKC 265 (trade name) manufactured by EKC Tedm〇1〇gy Inc., ACT 935 (trade name) manufactured by Ashland Chemical Co., Ltd., ELM C- manufactured by Mitsubishi Gas Chemical Co., Ltd. 30 (trade name)), which is used to remove the plasma etching by-product (residue) remaining after the plasma ashing remains due to the electric power. These products are also disclosed as patent documents (see Patent Document! - Patent Document 3, Patent Document 4). However, the pH of these commercially available products is as high as 11 or more, and contains a fluorine compound. Although the plasma etching residue can be effectively decomposed, there is a phenomenon in which the vapor deposition pattern of the metal or oxide on the substrate is also attacked. Although corrosion inhibitors are suitable for these products, it is difficult to obtain only sufficient corrosion prevention. In this regard, a cleaning composition which does not adversely affect the semiconductor substrate has been developed (see Patent Document 5 to Patent Document 7). It is a component of the water system C cleaning liquid, and contains an acid such as a hydroxylamine compound, a basic compound or an organic acid, and 201207100 can maintain the detergency from the surface, and the surface is prevented from being cured. In addition, the cleaning liquid is a water-based cleaning liquid which is a water-based medium, and is low in cost with respect to the organic cleaning liquid, and is excellent in environmental compatibility [Patent Document] [Patent Document 1] U.S. Patent No. 5,297,771 [Patent Document 2] U.S. Patent No. 5,419,779 [Patent Document 3] US Patent No. 563〇9〇4 [Patent Document 4] Japanese Patent No. 3891768 Specification 曰 [Patent Document 5] Japanese Patent [Patent Document 6] Japanese Patent No. 3,351,349 [Patent Document 7] Japanese Patent No. 414,732A (Invention), a new technology disclosed in Patent Documents 5 to 7, and a semiconductor The metal ship in the cleaning composition of the substrate is highly sturdy and high. However, the inventors of the present invention have continued to develop the ninth development in order to achieve higher performance. In particular, the following attempts have been made to promote the cleaning composition: the cleaning composition In a region where the specific cleaning agent exhibits a high detergency in a substantially neutral state, not only does the metal have high corrosion prevention, but also further develops A high corrosion prevention property of the present invention. It is an object of the present invention to provide a cleaning composition, a cleaning method using the same, and a method of manufacturing a semiconductor device which can be solved as being qualitatively adjusted to be neutral. Contains specific problems in specific and clear impurities, which can prevent the metal phase of the semi-conducting plate due to 6 201207100
JL 洗淨所造成之腐蝕，且可充分除去其製造步驟中所產生之 電漿钱刻殘渣或灰化殘渣。而且，其目的在於提供除了上 述優點以外，亦可同時實現源自水系清潔組成物之低成本 化及環境適合化的清潔組成物、使用其的洗淨方法及半導 體元件的製造方法。 上述碌通可藉由以下之手段而解決。 (1) 一種半導體基板用清潔組成物，實質上為中性， 其特徵在於含有： 水， 含氮化合物清潔劑， 驗性化合物， 1官能性、2官能性、3冑能性或4官能性之有機酸， 高分子化合物。 ⑵較佳的是如⑴所述之清潔組成物的所述高分 子化合物是選自由聚乙二醇、聚乙烯鱗伽、聚乙稀醇、 聚丙稀酸及輯㈣所構狀群組之至少丨種高分子化合 物。 σ 機酸2自較如⑴或（2)所叙清聽成物的有 :二i ^乳酸、乙酸、丙酸、蘋果酸、酒石 酉夂丙一 I、草酉夂、琥賴、葡萄糖酸、 酸、馬來酸、苯甲酸、齙婪一田雜^ 礼一己 及鄰茉#本—甲酸、水揚酸、柳異經肪酸 一、么辟酸（phthalhydroxamic acid )所構成之雜 組的至少1種化合物。 ⑴所構成之群 〇)中任一項所述之清潔組 (4)較佳的是如（1)〜 201207100 成物的鹼性化合物是碳數為4〜30之鹼性有機化合物。 (5) 較佳的是如（1)〜（4)中任一項所述之清潔組 成物的鹼性化合物是選自由有機胺及四級銨氫氧化物所構 成之群組的至少1種化合物。 (6) 較佳的是如（1)〜（5)中任一項所述之清潔組 成物的驗性化合物是不具羥基之有機胺。 (7) 較佳的是如（1)〜（6)中任一項所述之清潔組 成物的所述鹼性化合物是四烷基銨氫氧化物。 (8) 較佳的是如〜（7)中任一項所述之清潔組 成物的含氮化合物清潔劑是經胺化合物或胺甲酸化合物。 (9) 較佳的疋如（1)〜（8)中任一項所述之清潔組 成物的含氮化合物清潔劑是選自由羥胺、羥胺硫酸鹽、羥 胺鹽酸鹽、羥胺硝酸鹽及羥胺磷酸鹽所構成之群組的至少 1種化合物。 (10) 較佳的是如（1)〜（9)中任一項所述之清潔 組成物的所述含氮化合物清潔劑是羥胺硫酸鹽。 (11) 較佳岐如⑴〜（1G) +任—項所述之清潔 組成物用於除去半導體元件製造步驟巾之f漿侧殘渣及 /或灰化錄i杏。 (12)健的是藉心⑴〜（11)巾任—項所述之 =組成物而進行了洗淨的半導體基板包含露出之紹層或 (13):種洗淨方法，其特徵在於：藉由如⑴〜（η) 壬-項所述之清潔組成物對半導體基板上的電漿银刻殘 8 201207100 渣及/或灰化殘渣進行洗淨。 〜洗淨方法中，較佳的是於卿 如下導紅件的製造方法，其舰在於包含 (ϋ)飯刻步驟，對半導體基板進行電射虫刻， H 步驟’對半導體基板上之抗_進行灰 (b)洗淨步驟，藉由如⑴〜（12)中任 之清潔組成物’將於所述兹刻步驟及/或所述灰化步驟卜 體基板上所形成之電漿敍刻殘澄及/或灰化殘 [發明的效果] g Ϊ發明之清潔組成物可防止半導體基板之金屬層以及 L制J洗淨所造成之腐敍，且可充分除去於半導體元件 步驟中所產生之電_刻_或灰化紐。而且， 優點以外’亦可同時實現源自水系清潔組成物之 低成本化及環境適合化。 2外:藉由使用上述清潔組成物的本發明之洗淨方法 ，7L件的製造方法，可實現環境適應紅廉價地製 造尚品質之半導體元件。 為讓本發明之上述和其他目的、特徵和優點能更明顯 下文特舉較佳實施例，並配合所附圖式，作詳細說 明如下。 201207100 【實施方式】 明組成物是於水(a)中含有含氮化合物清 潔劑（b)、驗性有機化合物㈦、特定之 月 實質上被調整為中性之清潔組成物，其特徵在^含有^ m (e)°藉此可同時實現極其高的殘渣之洗淨； 與金屬之腐趣止性。關於其作用機制，推斷如下。 首先，於本發财，pH之選定非常重要，對此點加以 與之洗淨_胺等特衫氮化合物清潔劑的 1 酿之PKa處於特定之範圍，若清潔組成物之ph過於 =則洗淨？降低。另一方面，# pH過於變高，則洗淨 性f躍性f局。於僅考慮_之洗淨性能之情形時，較佳 ，是pH高。然而，若pH過高，則於金屬層等產生腐姓； 若pH超過9 ’則不能達成令人滿意之防錄能。 ’ 近年來，半導體元件之結構或適用部件進一步多樣 化’且小型化及微細配線化之要求日益提高。反映此種狀 況’於半導縣板之觀顧的洗料，亦嚴格要求對於 金屬層或矽層之腐蝕防止性的對應（於本發明中，於提及 石夕或石夕層時，表示包含魏化物（膜）或魏化物⑽） 等絕緣體（層）或半導體（層）>考慮此點，可列舉使酸 性化合物之量增加，降低清潔組成物之ρΗ而提高防蝕性。 然而，如果是這樣的話，於上述使用特定之含氮化合物清 潔劑的清潔組成物中，如上所述那樣不可避免地造成洗^ 力降低°於本發明中’採用克服該兩難困境（dilemma)， 將pH維持為中性區域，進一步於清潔組成物中含有特定 201207100 ,t 化合物（聚合物）的構成。由此進—步發現於實 性區域顺得的將上述特定錢化合物清潔劑的 =洗淨力維持為職，可同時達成金屬層財層之雜 防止性之提高。其作用原理尚包含不明點，但存在高分子 =合物所具有之疏水性質有所參麟可能性^如，於半 =體前驅物之表面成為疏水性之部分，其表面被高分子化 j包覆，形成與上述成分相互作狀特有的分子保護膜 、:構。以下，對於本發明之清潔組成物、使用其的洗淨方 法及半導體元件的製造綠讀佳實施職，參照一部分 圖式而加以詳細說明。 [殘渣] 於半導體元件之製造製程中，具有藉由將抗钱劑圖案 等用作遮罩的電_刻而對半導體基板上之金屬層等進行 钱^的步驟。具體而言’對金屬層、半導體層、絕緣層等 進行蝕刻，從而對金屬層或半導體層進行圖案化，或者於 絕緣層形成介層窗孔或配線溝等開口部α上述電毁钮刻 中，於半導體基板上生成源自用作遮罩之抗蝕劑或二 刻之金屬層、半導體層、絕緣層的魅。於本發明中被= 如上所述而由電漿蝕刻所產生之殘渣稱為「電漿蝕刻 渣」。 χ 而且，作為遮罩而使用之抗蝕劑圖案於蝕刻後被除 去。抗蝕劑圖案之除去可如上所述那樣使用如下之方法： 使用剝離劑溶液之濕式方法，或使用例如電漿、臭氧等之 灰化的乾式方法。於上述灰化中，於半導體基板上產生由 201207100 於電漿蝕刻所產生之電漿蝕刻殘渣變質而成的殘渣、或者 源自被除去之抗#劑之殘渣。於本發明中，將如上所述而 由於灰化所產生之殘渣稱為「灰化殘渣」。而且，作為電漿 触刻殘渣及灰化殘渣等在半導體基板上所產生之應被洗淨 除去者之總稱，有時僅稱為「殘渣」。 作為此種蝕刻後之殘渣（postEtchResidue)的電漿韻 刻殘渣或灰化殘渣較佳的是使用清潔組成物而洗淨除去。 本發明之清潔組成物特別適於作為用以除去由於電漿蝕刻 而產生之電漿蝕刻殘渣及/或由於灰化而產生之灰化殘渣 的/月潔組成物。本發明之清潔組成物亦可適用於用以除去 電漿蝕刻殘渣及/或灰化殘渣之洗淨方法（使用）中。其中， 較佳的是Μ於緊接著電放㈣進狀電敍化之後， 將電漿蝕刻殘渣及灰化殘渣除去。 [清潔組成物] 本發明之清潔組成物如上所述那樣於水中含有含氣化 。物清潔劑、祕有機化合物及特定之有機酸，且實質上 被调整為中性。以下，順次對各成分加 (水） t發明之清雜成物_水作為齡f，較佳的是各 ^有t分均勻地溶解之水料。㈣於清纽成物之總重 將t含量較佳的是50 wt%〜99 5 wt%。如上所述有 為水2為主成分（5Gwt%以上）之清潔組成物特別地稱 相比較二早=機溶劑之比率高的清潔組成物 乂更廉價且保§_竟之方面而言較佳。作為水，可 12 1 201207100 為於不損及本發明之效果之範圍包含溶解成分之水介質， 或者亦可包含不可避免之微量混合成分。其中，較佳的是 瘵餾水或離子交換水、或者被稱為超純水之實施了淨化處 理之水，特佳的是使用於半導體製造中所使用之超純水。 (含氮化合物清潔劑） 合物等。殘J 更佳的是C1 本發明之清潔組成物包含含氮化合物清潔劑（由含氮 原子之化合物所構成之清潔劑）。其中，該清潔劑較佳的是 胺化合物清潔劑（所謂胺化合物是氨、一級胺、二級胺、 二級胺、四級銨鹽、肟、包含=Ν·Η等之化合物的總稱）， 更佳的疋具有-ΝΗ2之胺化合物清潔劑，特佳的是具有· 且於分子内具有氧原子之胺化合物清潔劑。具體而言較佳 的是經胺（pKa=6)化合物、胺甲酸（carbamic add)化 羥胺之鹽較佳的是羥胺之無機酸鹽或有機酸鹽， 更佳的疋Cl、S、N、P等非金屬與驗結而成之無機酸之 鹽，特佳的疋鹽酸、硫酸、硝酸之任意酸之鹽。胺甲酸化 合物可列舉胺甲酸酯’其中較佳的是胺甲酸甲酯。 示包含羥基銨離子、 、羥胺及/或其鹽，典型的是表示鞀脸'JL is cleaned by corrosion and can sufficiently remove the residue or ash residue generated in the manufacturing process. Further, it is an object of the invention to provide a cleaning composition which is low in cost and environmentally compatible from a water-based cleaning composition, a cleaning method using the same, and a method for producing a semiconductor element, in addition to the above advantages. The above-mentioned rush can be solved by the following means. (1) A cleaning composition for a semiconductor substrate which is substantially neutral and which is characterized by comprising: water, a nitrogen-containing compound detergent, an organic compound, a monofunctional, a bifunctional, a trifunctional or a tetrafunctional Organic acid, polymer compound. (2) Preferably, the polymer compound of the cleaning composition according to (1) is at least selected from the group consisting of polyethylene glycol, polyethylene stellate, polyethylene glycol, polyacrylic acid, and series (4). A high molecular compound. σ 酸 2 is compared with the listener as described in (1) or (2): ii i lactic acid, acetic acid, propionic acid, malic acid, tartar 酉夂 I I, grass 酉夂, 琥 、, glucose Acid, acid, maleic acid, benzoic acid, 龅婪一田杂^ Li Yiji and Nei Mo #本—formic acid, salicylic acid, lyophilic acid, phthalhydroxamic acid At least one compound. (1) The cleaning group (4) according to any one of the above-mentioned groups, wherein the basic compound such as (1) to 201207100 is an alkaline organic compound having a carbon number of 4 to 30. (5) It is preferable that the basic compound of the cleaning composition according to any one of (1) to (4) is at least one selected from the group consisting of organic amines and quaternary ammonium hydroxides. Compound. (6) Preferably, the test compound of the cleaning composition according to any one of (1) to (5) is an organic amine having no hydroxyl group. (7) Preferably, the basic compound of the cleaning composition according to any one of (1) to (6) is a tetraalkylammonium hydroxide. (8) Preferably, the nitrogen-containing compound detergent of the cleaning composition according to any one of (7) is an amine compound or a urethane compound. (9) The nitrogen-containing compound detergent of the cleaning composition according to any one of (1) to (8), which is selected from the group consisting of hydroxylamine, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine nitrate and hydroxylamine. At least one compound of the group consisting of phosphates. (10) Preferably, the nitrogen-containing compound detergent of the cleaning composition according to any one of (1) to (9) is hydroxylamine sulfate. (11) Preferably, the cleaning composition according to (1) to (1G) + any of the items is used for removing the slurry side residue and/or ashing apricot of the semiconductor element manufacturing step. (12) The method of cleaning the semiconductor substrate which has been cleaned by the composition of the (1) to (11) towel, and includes the exposed layer or (13): a cleaning method, characterized in that: The plasma etch residue 8 201207100 slag and/or ash residue on the semiconductor substrate is washed by the cleaning composition as described in (1) to (η) 壬-. ~ Washing method, preferably is the manufacturing method of the following red-leading parts, the ship is included in the (ϋ) meal engraving step, electro-injection of the semiconductor substrate, H step 'anti-resistance on the semiconductor substrate _ Performing a ash (b) cleaning step, by using the cleaning composition as in any of (1) to (12), the plasma formation formed on the substrate and/or the ashing step substrate Residual and/or ashing residue [Effect of the invention] g The cleaning composition of the invention can prevent the metal layer of the semiconductor substrate and the ruin caused by the L-J cleaning, and can be sufficiently removed in the semiconductor element step. The electricity _ engraved _ or ash New Zealand. Further, in addition to the advantages, it is possible to simultaneously achieve cost reduction and environmental suitability of the water-based cleaning composition. 2: By the cleaning method of the present invention using the cleaning composition described above, the manufacturing method of the 7L member can realize the environment-adaptive red and inexpensive manufacture of a semiconductor element of a good quality. The above and other objects, features and advantages of the present invention will become more apparent from 201207100 [Embodiment] The composition is a cleaning composition containing a nitrogen-containing compound detergent (b) and an organic compound (7) in water (a), and is substantially adjusted to a neutral cleaning composition in a specific month, and is characterized in that Containing ^ m (e) ° to achieve extremely high residue cleaning at the same time; with metal rot. Regarding its mechanism of action, it is inferred as follows. First of all, in the case of this fortune, the choice of pH is very important, and this point is washed with _ amine and other special nitrogen compound detergents, the PKa of the brewing is in a specific range, if the cleaning composition is too ph = then wash net? reduce. On the other hand, when the pH is too high, the detergency f is f. In the case of considering only the washing performance, it is preferred that the pH is high. However, if the pH is too high, a rot is generated in the metal layer or the like; if the pH exceeds 9 Å, satisfactory anti-recording energy cannot be achieved. In recent years, the structure of semiconductor elements or applicable components have been further diversified, and the requirements for miniaturization and fine wiring have been increasing. In response to this situation, the washing of the semi-conducting plate is also strictly required for the corrosion prevention of the metal layer or the enamel layer (in the present invention, when referring to Shi Xi or Shi Xi layer, Insulator (layer) or semiconductor (layer) such as a weide (membrane) or a weide (10)) is considered. In view of this, the amount of the acidic compound is increased, and the pH of the cleaning composition is lowered to improve the corrosion resistance. However, if this is the case, in the cleaning composition using the specific nitrogen-containing compound cleaner described above, as described above, inevitably causing a decrease in the washing power. In the present invention, the use of the dilemma is overcome. The pH is maintained as a neutral region, and the composition of the specific 201207100, t compound (polymer) is further contained in the cleaning composition. As a result, it is found that the cleaning power of the specific money compound detergent is maintained in the solid area, and the prevention of the metal layer is simultaneously improved. The principle of action still contains an unknown point, but there is a possibility that the hydrophobic property of the polymer = compound has a possibility of arboring. For example, the surface of the semi-body precursor becomes hydrophobic, and the surface thereof is polymerized. It is coated to form a molecular protective film unique to the above components. Hereinafter, the cleaning composition of the present invention, the cleaning method using the same, and the manufacturing operation of the semiconductor device will be described in detail with reference to a part of the drawings. [Residue] In the manufacturing process of a semiconductor device, there is a step of charging a metal layer or the like on a semiconductor substrate by using an anti-money agent pattern or the like as a mask. Specifically, the metal layer, the semiconductor layer, the insulating layer, and the like are etched to pattern the metal layer or the semiconductor layer, or the opening portion α such as a via hole or a wiring trench is formed in the insulating layer. A metal layer, a semiconductor layer, and an insulating layer derived from a resist used as a mask or a second layer are formed on a semiconductor substrate. In the present invention, the residue generated by plasma etching as described above is referred to as "plasma etching slag". χ Moreover, the resist pattern used as a mask is removed after etching. The removal of the resist pattern can be carried out as follows: a wet method using a stripper solution, or a dry method using ashing such as plasma, ozone or the like. In the above ashing, a residue obtained by modifying the plasma etching residue generated by plasma etching in 201207100 or a residue derived from the removed anti-# agent is generated on the semiconductor substrate. In the present invention, the residue generated by ashing as described above is referred to as "ashing residue". Further, the term "plasma" may be referred to as a residue of a plasma-etched residue and an ashing residue which are to be washed and removed on a semiconductor substrate. It is preferable to use a cleaning composition as a plasma residue or an ash residue as a post-etch residue (resEtchResidue) to be washed and removed. The cleaning composition of the present invention is particularly suitable as a virgin composition for removing plasma etching residue due to plasma etching and/or ashing residue due to ashing. The cleaning composition of the present invention can also be suitably used in a cleaning method (use) for removing plasma etching residue and/or ashing residue. Among them, it is preferred that the plasma etching residue and the ash residue are removed immediately after the electric discharge (four) electric currentization. [Cleaning composition] The cleaning composition of the present invention contains vaporization in water as described above. A detergent, a secret organic compound, and a specific organic acid, and are substantially adjusted to be neutral. Hereinafter, it is preferable to add (water) to the respective components to the respective components, water, as the age f, and it is preferred that each of the components has a water content which is uniformly dissolved in t minutes. (4) Total weight of the compound in the Qing Dynasty The content of t is preferably 50 wt% to 99 5 wt%. As described above, there is a cleaning composition which is mainly composed of water 2 (5 Gwt% or more), and it is particularly preferable to use a cleaning composition having a high ratio of two early to machine solvent, which is cheaper and more preferable. . As the water, 12 1 201207100 may be an aqueous medium containing a dissolved component in a range that does not impair the effects of the present invention, or may contain an unavoidable trace mixed component. Among them, preferred are hydrazine water or ion-exchanged water, or water subjected to purification treatment called ultrapure water, and particularly preferred is ultrapure water used in semiconductor manufacturing. (nitrogen-containing compound detergent) and the like. More preferably, the cleaning composition of the present invention comprises a nitrogen-containing compound cleaner (a detergent composed of a compound containing a nitrogen atom). Among them, the detergent is preferably an amine compound cleaner (the so-called amine compound is ammonia, a primary amine, a secondary amine, a secondary amine, a quaternary ammonium salt, a ruthenium, a general term for a compound containing Ν·Η, etc.), More preferably, the oxime has an amine compound detergent of -2, and particularly preferably an amine compound cleaner having an oxygen atom in the molecule. Specifically, it is preferred that the amine (pKa=6) compound or the carbamic add hydroxylamine salt is preferably a mineral acid salt or an organic acid salt of hydroxylamine, more preferably 疋Cl, S, N, A salt of a non-metal such as P and a mineral acid which has been synthesized, and a salt of any acid of hydrochloric acid, sulfuric acid or nitric acid. The urethane compound may, for example, be a carbamate. Among them, a methyl carbamate is preferred. Included is a hydroxylammonium ion, a hydroxylamine, and/or a salt thereof, typically representing a face
於本說明書中提及化合物時，表示除了該化合物本身 以外’亦包含其鹽、其離子或其有機酸自旨。典型的是表示 該化合物及/或其鹽。因此，於提及上賴胺化合物時，表 13 201207100 羥胺之有機酸鹽，可例示羥胺檸檬酸鹽、羥胺草酸鹽等。 該些羥胺之射，雜顧鹽、_硫酸鹽、_^蹄°、 經胺鹽酸料無機酸賴於减銅、鈦#金屬而言隋 性’因此較佳。特別是經胺賴鹽、_硫酸鹽較二。該 些經胺化合物可單獨使用1誠者將2種以上混合使用Γ 於本發明中，清潔劑並不限定於上述經胺化合物，可 適宜選^具有所難之作用的化合物餘成物而使用。典 型的是：作為用以使魅成分料轉之作用，可列舉& 為親核劑而發揮功能的化合物。自該觀點考慮，可例示下 述化合物。 •較佳的是pKa為5以上8以下之親核劑（更佳的是 PKa為5.5以上7以下之親核劑） •具有α效果（若於α位具有供電子原子，則親核性 較根據pKa而預想的親核性更高）之親核劑 •Τι〇2之ER (蝕刻速率）高的親核劑 、較佳的是相對於本發明之清潔組成物之總重量而言， =約〇·〇ι wt%〜約30 wt%之範圍内含有含氛化合物清潔 你更佳的是含有ai wt%〜15 wt%。清潔劑特別顯示出 ^電聚钱刻雌之除去變容易，防止金屬基板之腐姓的作 藉由設為上述範圍，可特別適宜發揮高的洗淨力，且 分獲得良好之金屬腐蝕防止效果，於該方面而言較佳。 &生另外，於本發明中，較佳的是不含氟化銨等含氟化合 :潔劑。其在於：錢化合物清潔劑經常具有金屬 I切層之腐錄，料使獲得洗淨力，亦難以確保金屬 201207100 層或矽層之充分之耐腐蝕性。 (驗性化合物） 本發明之/月潔組成物包含驗性化合物。於本發明中、 所》月驗1±化合物」表示並不包含上輸胺化合物或胺曱 酉夂化合物，且並不__化合物作為該「驗性化合物」。 驗性化合物難的是驗財機化合物。健的是具有碳及 IU乍為其構成元素，更麵是具有縣。具體^言，驗性 有機化合物健的是選自有機胺及四級銨氫氧化物所構成 之群組的至少1種化合物。糾，所謂有_是表示包含 碳作為構成元素的胺。 鹼性有機化合物之碳數較佳的是4〜3〇，自沸點或於 水中之溶解度之觀點考慮更佳的是6〜16。 作為本發明之清潔組成物之驗性有機化合物而使用的 有機胺包含：單乙醇胺、二乙醇胺、三乙醇胺、二乙二醇 胺、N-羥基乙基哌嗪等烷醇胺，及/或乙胺、苯曱胺、二乙 基fe、正丁基胺、3-曱氧基丙基胺、第三丁基胺、正己基 胺、環己胺、正辛基胺、2-乙基己基胺、鄰二曱苯二胺、 間二曱苯二胺、^曱基丁基胺、乙二胺（EDA)、1，3-丙二 胺、2-胺基苯甲胺、N-苄基乙二胺、二乙三胺、三乙四胺 等不具羥基之有機胺。自金屬之腐蝕防止之觀點考慮，不 具羥基之有機胺較烷醇胺更佳。另外，乙二胺、u_丙二 胺、鄰二甲苯二胺、間二甲苯二胺可與金屬配位而特佳。 作為鹼性化合物而使用之四級銨氫氧化物較佳的是四 烷基銨氫氧化物，更佳的是經低級（碳數為1〜4)烷基取 15 201207100 代之四絲錄氫氧化物，具體而言可列舉氫氧化四甲基敍 (TMAH)、氫氧化四乙基銨（TEAH)、絲化四丙^錄 (ΤΡΑΗ)、氫氧化四丁基銨（ΤΒΑΗ)等。另外，四級銨 氫氧^物亦可列舉氫氧化三曱紐乙基録（膽驗）、氫氧化 曱基三(經乙基)錄、氫氧化四(經乙基)録、氫氧化节基三甲 基錢（ΒΤΜΑΗ)等。除此以外，亦可使用氫氧化録與i 種或1種以上四級銨氫氧化物之組合。該些中更佳的是 TMAH、TEAH、TPAH、TBAH、膽鹼，特佳的是 TMAH、 TBAH。 該些有機胺及四級銨氫氧化物可單獨使用丨種或者將 2種以上混合使用。 相對於本發明之清潔組成物之總重量，鹼性化合物之 s量較佳的是約〇 〇1 wt%〜約20.0 wt%，更佳的是1 .〇 wt〇/0 〜10·0 wt°/〇。藉由設為上述範圍，可與上述之羥胺化合物 等特定之含氮化合物清潔劑之含量對應，充分發揮pH調 整作用’同時實現高的洗淨力與金屬腐蝕防止效果，因此 較佳。 (有機酸） 本發明之清潔組成物含有至少1種有機酸（亦稱為酸 性有機化合物），例如為1官能性、2官能性、3官能性或 4官能性有機酸。官能基之數並無特別之限定，其中較佳 的是1官能性或2官能性或3官能性。 有機酸中’羧酸化合物可有效地防止鋁、銅及該些之 合金之金屬腐蝕而較佳，具有羥基之羥基羧酸化合物可特 16 201207100, 別有效地防止金屬腐飯而更佳。緩酸化合物對於該些金屬 具有螯合效果。較佳之羧酸化合物包含單竣酸化合物及多 羧酸化合物。羧酸化合物並不限定於該些化合物，可例示 甲酸、乙酸、丙酸、戊酸、異戊酸、草酸、丙二酸、琥珀 酸、戊二酸、馬來酸、富馬酸、鄰苯二甲酸、以》苯三曱 酸、乙醇酸、乳酸、檸檬酸、水揚酸、酒石酸、葡萄糖酸、 氧二乙酸、蘋果酸、乙醯異羥肟酸、笨曱羥肟酸、柳異羥 肟酸、鄰苯二甲異羥肟酸、苯曱酸、二羥基苯曱酸及該些 之混合物。其中可較佳地使用作為羥基羧酸之檸檬酸、蘋 果酸、酒石酸、乙醇酸、葡萄糖酸、乳酸。 另外，羧酸化合物較佳的是構成元素僅為C、H及〇， 更佳的是不具胺基。 而且，該些有機酸可單獨使用i種或者將2種以上混 ，使用，但自有效地防止金屬之腐蝕之觀點考慮，較佳的 是併用2種以上。相對於本發明之清潔組成物之總重量， ，佳的是於約G.G1 wt%〜約2G.G wt%之間添加酸性有機化 合物，更佳的是添加約0.05 wt%〜約2〇 〇wt%，進一步更 佳1是添加0.1 wt%〜1〇 〇 wt%。藉由設為上述範圍，可與 羥胺化合物及鹼性有機化合物之上述較佳之含量對應，並 减洗淨力降低地充分獲得良好之金顧赌止效果，於 此方面而言較佳。另外，有機酸之定義與所述「化合物」 同樣，是包含其鹽等之概念。 (清潔組成物之pH) 本發明之清潔組成物實質上被調整為中性。於本發明 17 201207100. 中質上為中性是指於可起到清潔組成物之所期望 二66 3巳if内’該組成物的阳處於7附近。具體之ΡΗ ^〜^，口〜^更佳的是’^進—步更佳的是 .· 的疋7.2〜8.0。若pH為上述數值範圍内， 則可^分地除去光阻#卜抗反賴、綱魅及灰化殘渣 且同時兼顧金屬之防钱。藉由設為該pH範圍，可充分除 去對氮化⑪與金；|層進行電漿似彳而形成介層窗圖案之 形時的殘遣’因此較佳。作為pH之測定方法，可使用市 售之PH計而進行測定1本發明中，若無特別之限定， 則pH是指於實例中所示之條件下測定之值。為了將清潔 組成物調整為規定之pH’可藉由調節驗性有機化合物之添 加量的滴定而進行。 (高分子化合物） 一本發明之清潔組成物除了所述基本成分以外，亦含有 咼分子化合物。該高分子化合物並無特別之限定，較佳的 是可均勻地分散或溶解於水介質中的高分子化合物，更佳 的是以規定之含量均勻地溶解之高分子化合物。具體而言 可列舉聚乙二醇、聚乙稀咖各咬_、聚乙稀醇、聚丙烯酸' 聚乙稀亞胺、多盼、或聚烯丙胺4中較佳的是聚乙婦呢 咯啶酮、聚乙二醇、聚乙烯醇。高分子化合物之分子量並 無特別之限定，較佳的是400〜30冑，更佳的是5〇〇〇〜 90000。若分子量小’則無法獲得令人滿意之防蝕性。而且， 若分子量過大，則雖然可達成防蝕性，但有損洗淨性。 於本發明中，於提及分子量時，若無特別限制則表示 18 201207100 a. 重量平均分子量，分子量及分散度是指藉由下述之測定方 法而測定之值。 [分子量、分散度之測定方法] 、刀子量及分散度若無特別限制，則可使用GPC (凝膠 過遽層析）法it行測定。GP C法巾所使狀管柱巾所填^ 的凝膠較佳的是於重複單元巾具有芳香族化合物的凝膠， 例如可列舉由苯乙烯_二乙烯基苯共聚物所構成之凝膠。管 板較佳的疋使2根〜6根連結而使用。所使用之溶劑可列 舉四氫呋喃等醚系溶劑、N-曱基吡咯啶酮等醯胺系溶劑， 較佳的是四氫呋喃等醚系溶劑。較佳的是於溶劑之流量為 0·1 mL/min〜2 mL/min之範圍内進行測定，最佳的是於〇 5 UiL/min〜1.5 mL/min之範圍内進行測定。藉由於該範圍内 進行測定，可不對裝置造成負荷，更有效率地進行測定。 較佳的是於測定溫度為10°C〜50°C下進行，最佳的是於 2〇°c〜4〇〇C下進行。 以下表示分子量測定之具體條件。 裝置：HLC-8220GPC (東曹股份有限公司製造） 檢測器：示差折射儀（RI檢測器） 前置管柱：TSKGUARDCOLUMN MP ( XL ) 6 mm><40 mm (東曹股份有限公司製造） 樣品侧管柱：直接連結以下2根（均為東曹股份有限 公司製造） • TSK-GEL Multipore-HXL-M 7.8mmx300mm 參考侧管柱.與樣品側管柱相同 201207100 恆溫槽溫度：40°C 移動床：四氫吱〇南 樣品侧移動床流量：l.〇mL/min 參考側移動床流量：0.3mL/min s式樣濃度：0.1 wt%When a compound is referred to in the specification, it means that a salt thereof, an ion thereof or an organic acid thereof is contained in addition to the compound itself. Typically, the compound and/or its salt is represented. Therefore, when referring to the upper lysine compound, the organic acid salt of hydroxylamine of Table 13 201207100 can be exemplified by hydroxylamine citrate, hydroxylamine oxalate or the like. The shots of the hydroxylamines are preferably referred to as salts, sulphates, shovels, minerals by amines and hydrochloric acids, and by copper and titanium. In particular, it is better than amine lysine and _ sulphate. These amine-containing compounds may be used alone or in combination of two or more. In the present invention, the detergent is not limited to the above-mentioned amine compound, and may be suitably selected from a compound having a difficult function. . Typically, as a function for transferring the fascinating component, a compound which functions as a nucleophile can be cited. From the viewpoint of this, the following compounds can be exemplified. • A nucleophile having a pKa of 5 or more and 8 or less (more preferably a nucleophile having a PKa of 5.5 or more and 7 or less) is provided. • It has an α effect (if an electron donor atom is present at the α position, the nucleophilicity is higher. a nucleophile having a higher nucleophilicity (preferably based on pKa), a nucleophile having a high ER (etching rate) of Τι〇2, preferably relative to the total weight of the cleaning composition of the present invention, About 〇·〇ι wt%~ about 30 wt% of the range containing the compound containing the cleaning you better is containing ai wt% ~ 15 wt%. In particular, the cleaning agent shows that it is easy to remove the electric engraving and prevent the corrosion of the metal substrate from being made into the above range, and it is particularly suitable to exhibit a high detergency and obtain a good metal corrosion prevention effect. It is preferred in this respect. Further, in the present invention, it is preferred that the fluorine-containing compound such as ammonium fluoride is not used. It is that the money compound cleaner often has a corrosion of the metal I layer, which is used to obtain a detergency, and it is also difficult to ensure sufficient corrosion resistance of the metal layer 201207100 or the layer. (Experimental Compound) The composition of the present invention comprises an inspective compound. In the present invention, the "monthly test compound" means that the upper amine compound or the amine ruthenium compound is not contained, and the __ compound is not used as the "test compound". It is difficult to test compound compounds. It is made up of carbon and IU乍 as its constituent elements, and it has a county. Specifically, the organic compound is at least one compound selected from the group consisting of an organic amine and a quaternary ammonium hydroxide. Correction, the so-called _ is an amine containing carbon as a constituent element. The carbon number of the basic organic compound is preferably 4 to 3 Å, and more preferably 6 to 16 from the viewpoint of boiling point or solubility in water. The organic amine used as the organic compound for cleaning the composition of the present invention comprises: an alkanolamine such as monoethanolamine, diethanolamine, triethanolamine, diethylene glycolamine or N-hydroxyethylpiperazine, and/or Amine, benzoguanamine, diethyl fe, n-butylamine, 3-methoxypropylamine, tert-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, 2-ethylhexylamine , o-diphenylene diamine, m-diphenylene diamine, decyl butylamine, ethylenediamine (EDA), 1,3-propanediamine, 2-aminobenzylamine, N-benzyl An organic amine having no hydroxyl group such as diamine, diethylenetriamine or triethylenetetramine. From the viewpoint of corrosion prevention of metals, an organic amine having no hydroxyl group is more preferable than an alkanolamine. Further, ethylenediamine, u-propylenediamine, o-xylenediamine, and m-xylenediamine may be particularly preferably coordinated to a metal. The quaternary ammonium hydroxide used as the basic compound is preferably a tetraalkylammonium hydroxide, and more preferably a lower (carbon number of 1 to 4) alkyl group 15 201207100 Specific examples of the oxide include tetramethyl hydride (TMAH), tetraethylammonium hydroxide (TEAH), silk fibroin (tetrahydrocarbazine), and tetrabutylammonium hydroxide (hydrazine). In addition, the quaternary ammonium hydroxide can also be exemplified by triammonium hydroxide (bi-test), ruthenium hydroxide-based (by ethyl), tetra-hydrogen (by ethyl), and hydroxide Base trimethyl money (ΒΤΜΑΗ) and so on. In addition to this, a combination of a hydroxide or a type of one or more quaternary ammonium hydroxides may also be used. More preferred among these are TMAH, TEAH, TPAH, TBAH, choline, and particularly preferred are TMAH, TBAH. These organic amines and quaternary ammonium hydroxides may be used singly or in combination of two or more. The amount of the basic compound is preferably from about 1% by weight to about 20.0% by weight based on the total weight of the cleaning composition of the present invention, more preferably 1. 〇wt〇/0 〜10·0 wt °/〇. By setting it as the above-mentioned range, the pH adjustment effect can be sufficiently exhibited in accordance with the content of the specific nitrogen-containing compound detergent such as the above-described hydroxylamine compound, and a high cleaning power and a metal corrosion prevention effect can be achieved, which is preferable. (Organic acid) The cleaning composition of the present invention contains at least one organic acid (also referred to as an acid organic compound), and is, for example, a monofunctional, bifunctional, trifunctional or tetrafunctional organic acid. The number of functional groups is not particularly limited, and among them, preferred is monofunctional or bifunctional or trifunctional. The 'carboxylic acid compound in the organic acid is effective for preventing corrosion of aluminum, copper and metals of the alloys, and the hydroxycarboxylic acid compound having a hydroxyl group is particularly useful as a metal rot. The acid retarding compound has a chelation effect on the metals. The preferred carboxylic acid compound comprises a monodecanoic acid compound and a polycarboxylic acid compound. The carboxylic acid compound is not limited to these compounds, and examples thereof include formic acid, acetic acid, propionic acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, and o-benzene. Dicarboxylic acid, phthalic acid, glycolic acid, lactic acid, citric acid, salicylic acid, tartaric acid, gluconic acid, oxydiacetic acid, malic acid, acetohydroxamic acid, alum hydroxy citric acid, willow hydroxy Capric acid, phthalic acid, benzoic acid, dihydroxybenzoic acid, and mixtures thereof. Among them, citric acid, malic acid, tartaric acid, glycolic acid, gluconic acid, and lactic acid which are hydroxycarboxylic acids can be preferably used. Further, the carboxylic acid compound preferably has a constituent element of only C, H and hydrazine, and more preferably has no amine group. Further, these organic acids may be used alone or in combination of two or more. From the viewpoint of effectively preventing corrosion of metals, it is preferred to use two or more kinds in combination. Preferably, the acidic organic compound is added between about G.G1 wt% and about 2 G.G wt%, more preferably about 0.05 wt% to about 2 Torr, relative to the total weight of the cleaning composition of the present invention. 〇wt%, further better 1 is to add 0.1 wt% to 1% by weight. By setting it as the above range, it is preferable to obtain a good gambling effect in accordance with the above-mentioned preferable content of the hydroxylamine compound and the basic organic compound, and to reduce the cleaning power. Further, the definition of the organic acid is the same as the "compound" described above, and is a concept including a salt thereof. (pH of cleaning composition) The cleaning composition of the present invention is substantially adjusted to be neutral. In the present invention, 17 201207100. Neutral in neutrality means that it is desirable to clean the composition. The cation of the composition is in the vicinity of 7. Specifically ΡΗ ^ ~ ^, mouth ~ ^ better is '^ into the step is better. 疋 7.2 ~ 8.0. If the pH is within the above numerical range, the photoresist can be removed in abundance, and the metal and the ashing residue can be simultaneously taken care of. By setting it as the pH range, it is possible to sufficiently remove the remnant when the nitride layer 11 and the gold layer are plasma-like to form a via pattern. The measurement method of the pH can be carried out by using a commercially available pH meter. In the present invention, the pH is a value measured under the conditions shown in the examples unless otherwise specified. The adjustment of the cleaning composition to a predetermined pH' can be carried out by adjusting the titration of the additive amount of the organic compound. (Polymer Compound) A cleaning composition of the present invention contains a ruthenium molecular compound in addition to the essential component. The polymer compound is not particularly limited, and is preferably a polymer compound which can be uniformly dispersed or dissolved in an aqueous medium, and more preferably a polymer compound which is uniformly dissolved in a predetermined amount. Specifically, polyethylene glycol, polyethylene coffee, bite _, polyethylene glycol, polyacrylic acid 'polyethylene imimine, poly hope, or polyallylamine 4 are preferred. Pyridone, polyethylene glycol, polyvinyl alcohol. The molecular weight of the polymer compound is not particularly limited, and is preferably 400 to 30 Å, more preferably 5 Å to 90000. If the molecular weight is small, satisfactory corrosion resistance cannot be obtained. Further, if the molecular weight is too large, the corrosion resistance can be achieved, but the detergency is impaired. In the present invention, when the molecular weight is referred to, unless otherwise specified, it means 18 201207100 a. The weight average molecular weight, molecular weight and degree of dispersion refer to values measured by the following measurement methods. [Method for Measuring Molecular Weight and Dispersion] The amount of the knife and the degree of dispersion are not particularly limited, and can be measured by GPC (gel over chromatography). The gel filled with the lining of the GP C towel is preferably a gel having an aromatic compound in the repeating unit, and for example, a gel composed of a styrene-divinylbenzene copolymer may be mentioned. . The tube plate is preferably used by connecting two to six pieces. The solvent to be used may, for example, be an ether solvent such as tetrahydrofuran or a guanamine solvent such as N-decylpyrrolidone, and an ether solvent such as tetrahydrofuran is preferred. Preferably, the measurement is carried out at a flow rate of the solvent of from 0.1 mL/min to 2 mL/min, and most preferably in the range of from 5 UiL/min to 1.5 mL/min. By performing measurement in this range, it is possible to perform measurement more efficiently without burdening the device. It is preferably carried out at a measurement temperature of from 10 ° C to 50 ° C, most preferably at 2 ° C to 4 ° C. The specific conditions for molecular weight measurement are shown below. Device: HLC-8220GPC (manufactured by Tosoh Corporation) Detector: differential refractometer (RI detector) Front column: TSKGUARDCOLUMN MP (XL) 6 mm><40 mm (manufactured by Tosoh Corporation) Side pipe column: directly connect the following two (all manufactured by Tosoh Corporation) • TSK-GEL Multipore-HXL-M 7.8mmx300mm reference side pipe column. Same as sample side pipe column 201207100 Temperature bath temperature: 40°C movement Bed: tetrahydrofuran sample side moving bed flow: l. 〇mL / min reference side moving bed flow: 0.3mL / min s pattern concentration: 0.1 wt%
試樣注入量：l〇〇pL 資料採集時間：試樣注入後16 min〜46 min 取樣間距：300msec 上述高分子化合物可單獨使用1種或者將2種以上混 合使用。相對於本發明之清潔組成物之總重量，較佳的是 於3 wt%〜0.000001 wt%之間添加高分子化合物，更佳的 是添加1 wt%〜0.000001 wt%，進一步更佳的是添加〇1 Wt%〜0.0001 wt%。藉由設為上述範圍，於維持高的洗淨 力而充分獲得良好之金屬及矽之腐蝕防止效果之方面而t 較佳。該高分子化合物可藉由使其含量增加而進—二 蝕性提高。然而過度之含量變得有損洗淨能力。 (水溶性有機溶劑） 本發明之清潔組成物亦可含有水溶性有 性有機溶撕腐倾止方面而讀佳，如可=甲=溶 乙醇、1-丙醇、2-丙醇、2_丁醇、乙二醇醇、 ?、1，6-己二醇、環己二醇、山梨糖醇、木糖醇、；甲旯:三 戊二酵、i，3_丁二醇、M_丁二醇等醇系溶劑，乙二=，4-醚、二乙二醇、二丙二醇、丙二醇單甲蜒、 -旱甲 醚、三乙二醇、聚乙二醇、丙二醇單 一乙一醇單甲 7醚、二丙二醇單甲 201207100, 醚、三丙二醇單甲醚、二乙二醇單丁醚等醚系溶劑，曱醯 胺、單甲基甲醯胺、二曱基曱醯胺、乙醯胺、單甲基乙醯 胺、二曱基乙醯胺、單乙基乙醯胺、二乙基乙醯胺、队曱 基吼洛咬酮等醯胺系溶劑，二曱基颯、二曱基亞硬、環丁 石風等含硫系溶劑，γ· 丁内醋、δ_戊内醋等内醋系溶劑等。 該些溶劑中較佳的是醇系、醚系，更佳的是丨,6-己二醇、 二乙二醇、丙二醇、二丙二醇、丙二醇單曱醚、二丙二醇 單曱醚。水溶性有機溶劑可單獨使用亦可將2種以上適宜 組合而使用。 清潔組成物中之水溶性有機溶劑之含量相對於清潔組 成物之總重量而言，較佳的是以Owt%〜40 wt%之濃度使 用，更佳的是以〇 wt%〜20 wt%之濃度使用。進一步更佳 的是以0.01 wt%〜15 wt%之濃度使用。藉由將水溶性有機 溶劑添加於清潔組成物中，可提高對於富碳殘渣之洗淨 力，而且自提高金屬膜之腐蝕防止性之觀點考慮亦較佳。 (其他成分） •含胺基之羧酸化合物 本發明之清潔組成物另外亦可含有含胺基之羧酸化合 物。含胺基之羧酸化合物於效率良好地防止金屬腐蝕之方 面而言較佳。含胺基之羧酸化合物中，較佳的是精胺酸、 組胺酸、麩醯胺、£0丁八、0丁?八、1110入，更佳的是精胺酸、 組胺酸。該些含胺基之敌酸化合物可單獨使用1種或者可 將2種以上混合使用。於本發明之清潔組成物中含有含胺 基之羧酸化合物之情形時，其添加量可適宜選擇，相對於 21 201207100 本發明之清潔組成物之總重量，較佳的是約讀wt%〜約 5·0 wt% ’ 更佳的是 〇 〇1 wt%〜3 wt〇/〇。 •界面活性劑 而且’本發明之清潔組成物亦可含有界面活性劑。界 面活性劑可使用非離子性、陰離子性、陽離子性界面活性 劑及兩性界Φ活㈣Η目對於清練成物之總重量，清潔 組成物中之界面活性劑之含量較佳的是〇 _ wt%〜5 wt% ’更佳的是〇·〇_㈣❶叫wt%。藉由將界面活性劑添 加於清潔組成物巾，可織清潔組成物之織，且改良對 於清潔對象物之賴性，因此雛，進—步自對於基板或 絕緣膜等之腐錄此兩者更優異之方面考慮亦較佳。此種 界面活f·生劑通吊可商業性獲得。該些界面活性 用或者多種組合使用。 •防黴劑 本發明之清潔組成物亦可含有防黴劑。腐钱抑制劑較 佳的是雜環化合物，更㈣是苯幷三錢其魅物。所述 衍生物較佳的是5,6-二曱基H3·苯幷***（Dbta)、 1·(1，2-二羧基乙基)苯幷***（DCEBTA)、•雙(羥乙 基)胺基甲基]苯幷***（ΗΕΑΒΤΑ)、^(羥基曱基)苯幷三 嗤（ΗΜΒΤΑ)。本發明中所使用之防黴劑可單獨使用，亦 可併用2種以上。而且，本發明中所使用之防黴劑除了依 照通用方法而合成以外，亦可使用市售品。而且，防黴劑 之添加量較佳的是〇.〇1 wt%以上0.2 wt%以下，更佳的是 0.05 wt%以上 〇·2 wt% 以下 〇 22 201207100Sample injection amount: l〇〇pL Data acquisition time: 16 min to 46 min after sample injection Sampling pitch: 300 msec The above polymer compounds may be used singly or in combination of two or more. Preferably, the polymer compound is added between 3 wt% and 0.000001 wt%, more preferably 1 wt% to 0.000001 wt%, more preferably added, relative to the total weight of the cleaning composition of the present invention. 〇1 Wt%~0.0001 wt%. By setting it as the above range, it is preferable to maintain a high cleaning power and sufficiently obtain a good metal and anticorrosive effect. The polymer compound can be improved by increasing its content. However, excessive levels become detrimental to the ability to clean. (Water-Soluble Organic Solvent) The cleaning composition of the present invention may also contain a water-soluble organic soluble tearing rot, and may be read as follows, such as = A = ethanol, 1-propanol, 2-propanol, 2_ Butanol, ethylene glycol alcohol, ?, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, formazan: triamyl glycol, i, 3-butanediol, M_ Alcohol solvent such as butanediol, ethylene-2, 4-ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl hydrazine, - dry methyl ether, triethylene glycol, polyethylene glycol, propylene glycol, single ethyl alcohol monomethyl 7 ether, dipropylene glycol monomethyl 201207100, ether solvent such as ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, decylamine, monomethylformamide, dimethyl decylamine, acetamide , monomethyl acetamide, dimercaptoacetamide, monoethyl acetamide, diethyl acetamide, guanidine ketone ketone and other amide solvent, dimercapto ruthenium, dihydrazino A sulfur-containing solvent such as a sub-hard or a ring-shaped stone, a vinegar solvent such as γ·butyrolactone or δ_pentane vinegar. Preferred among these solvents are alcohol-based and ether-based, and more preferred are hydrazine, 6-hexanediol, diethylene glycol, propylene glycol, dipropylene glycol, propylene glycol monodecyl ether, and dipropylene glycol monoterpene ether. The water-soluble organic solvent may be used singly or in combination of two or more kinds as appropriate. The content of the water-soluble organic solvent in the cleaning composition is preferably from 0% by weight to 40% by weight based on the total weight of the cleaning composition, more preferably from 〇wt% to 20% by weight. Concentration is used. Further preferably, it is used in a concentration of from 0.01 wt% to 15 wt%. By adding a water-soluble organic solvent to the cleaning composition, the cleaning power for the carbon-rich residue can be improved, and it is also preferable from the viewpoint of improving the corrosion prevention property of the metal film. (Other components) • Amino group-containing carboxylic acid compound The cleaning composition of the present invention may further contain an amine group-containing carboxylic acid compound. The amine group-containing carboxylic acid compound is preferred in terms of efficiently preventing metal corrosion. Among the amino group-containing carboxylic acid compounds, preferred are arginine, histidine, glutamine, butyl ketone, 0 butyl octagonal, and 1110, and more preferred are arginine and histidine. These amine group-containing acid compounds may be used singly or in combination of two or more. In the case where the cleaning composition of the present invention contains an amine group-containing carboxylic acid compound, the amount thereof may be appropriately selected, and it is preferably about wt% of the total weight of the cleaning composition of the present invention with respect to 21 201207100. About 5.00 wt% is more preferably 〇〇1 wt%~3 wt〇/〇. • Surfactant and The cleaning composition of the present invention may also contain a surfactant. The surfactant can be used as a nonionic, anionic, cationic surfactant and amphoteric Φ live (4). For the total weight of the clarified product, the content of the surfactant in the cleaning composition is preferably 〇 _ wt %~5 wt% 'Better is 〇·〇_(4) ❶ wt%. By adding a surfactant to the cleaning composition towel, the weaving of the composition can be woven, and the adhesion to the object to be cleaned can be improved, so that the two are further recorded from the substrate or the insulating film. The more excellent aspects are also considered. Such an interface activity can be obtained commercially. These interfacial activities are used in combination or in various combinations. • Antifungal Agent The cleaning composition of the present invention may also contain an antifungal agent. The preferred ones are the heterocyclic compounds, and the more (4) are the benzoquinones. The derivative is preferably 5,6-dimercapto H3.benzotriazole (Dbta), 1 (1,2-dicarboxyethyl)benzotriazole (DCEBTA), • double (hydroxyl) Aminomethyl]benzoquinone triazole (ΗΕΑΒΤΑ), ^(hydroxydecyl)benzoquinone triterpene (ΗΜΒΤΑ). The antifungal agent used in the present invention may be used singly or in combination of two or more. Further, the antifungal agent used in the present invention may be synthesized in accordance with a general method, and a commercially available product may be used. Further, the amount of the antifungal agent added is preferably wt. 〇1 wt% or more and 0.2 wt% or less, more preferably 0.05 wt% or more 〇·2 wt% or less 〇 22 201207100
_ L 各成分之組成物令之鑑定可藉由通用方法而適宜地進 行’例如可使用離子層析法或H_NMR、分光吸收度計。 [洗淨方法] 又 其次，對本發明之洗淨方法之較佳之實施形態加以說 明。本實施形態之洗淨方法是包含洗淨步驟的方法，所述 洗淨步驟是使用上述本發明之清潔組成物，對形成於半導 體基板上之電漿蝕刻殘渣及/或灰化殘渣進行洗淨。於該洗 淨方法中，於有效地發揮作為上述本發明之清潔組成物之 優點的高的洗淨力與金屬層或矽層之腐蝕防止性的方面而 言，較佳的是於半導體基板中’形成例如介層窗（via)或 配線等之金屬層而露出，於此處堆積上述殘渣之狀態。作 為金屬層，包含鋁或銅之金屬層可發揮上述本發明之清潔 組成物之效果，因此更佳。所述洗淨步驟中之洗淨之態樣 若為使至少形成有電漿钮刻殘潰及/或灰化殘渣之半導體 基板之面與本發明之清潔組成物接觸之態樣，則並無特別 之限疋較佳的疋將該半導體基板浸潰於本發明之清潔組 成物中之態樣。 ’ 本實施形態之洗淨方法較佳的是於上述洗淨步驟中， 於清潔組成物被加熱之狀態下進行。清潔組成物之洗淨步 驟中的加熱溫度並無特別限定，較佳的是50°c〜90°c，更 佳=是55°C〜80°C。因此，藉由本實施態樣，於如上所述 之範圍内對組成物進行加熱而使用，因此較佳的是含有成 分不於該溫度下分解、揮發、反應之化合物。而且，較佳 的是由於溫度之組成物之pH變化並不大，於上述實施形 23 201207100 態之清潔組成物_’於自室溫至上述洗淨時之溫度中 之變化並不大且實質上為中性。 [半導體元件的製造方法] 其次，對本發明之半導體元件的製造方法之較佳實施 形‘i加以詳述。本實麵態㈣造方法包含如下步驟： (a_l)側步驟，對半導體基板進行電㈣刻，及/或（ 灰化步驟，對半導體基板上之抗_進行灰化；以及㈦ 驟’藉由如上狀清潔組成物，將於所舰刻步驟 t l f 射，於所料導縣板上所形成之電浆 银刻殘歧/歧化_洗淨除去。具體㈣，較佳^ 形成介層窗孔或g&線後之轉祕板之洗料，適用上述 清潔組成物之製造方法。另外，本發明中之所謂「半導= 基板」是指於製造半導體元件（最終產品）之中途的 中1半導體元件前驅物)’若無特別之限定，則表 不不僅僅切晶圓，亦包含例如_ 緣膜或鎢插塞、介層窗孔、配線等者。域有層間絕 (第1實施形態） 離之是表示基於本發明之第1實施形 導财置的製以法之概要的步 圖1(0〜圖3⑷是設想剖面而表示的，為^夕卜 之繁雜’省略剖面線（hatching)而進行表示、。 •步驟a:參照圖1 (a) μ 蓉本=其f由通常之半導體裝置之製造製程，於石夕晶圓 4半導體基板10上形成雷sβ廿，， 圓 域電日日體及其他的元件或1層或2 24 201207100 二其次於形成有元件等之半導體基板10 '日、、、膜。其次，藉由例如 CVD( Chemical Vapor 厘Π1:"化學軋相沈積)法，於整個面順次積層例如膜 暄，之A1合金膜12、例如膜厚約50腿之氮化鈦 而点成順次積層有A1合金膜12與氛化欽膜14 而成^導體膜。另外’ A1合金㈣是例如含有〇3加％〜 wt/o之Cu的A1與Cu之合金膜。 料雜f彡法及乾式_料舰進行圖案 /ιό ^A1合金膜12與氮化鈦膜14所構成之配 ί 1 ^ 如CVD法’於整個面形成例如膜厚 ^ 5 CMp(ChemicalThe composition of each component of L may be suitably determined by a general method. For example, ion chromatography or H_NMR or a spectrosorber can be used. [Washing method] Next, a preferred embodiment of the washing method of the present invention will be described. The cleaning method of the present embodiment is a method including a cleaning step of cleaning the plasma etching residue and/or the ash residue formed on the semiconductor substrate by using the cleaning composition of the present invention described above. . In the cleaning method, in order to effectively exhibit the high cleaning power which is the advantage of the cleaning composition of the present invention and the corrosion prevention property of the metal layer or the tantalum layer, it is preferably in the semiconductor substrate. A metal layer such as a via or a wiring is formed and exposed, and the residue is deposited therein. As the metal layer, the metal layer containing aluminum or copper can exert the effect of the above-described cleaning composition of the present invention, and therefore is more preferable. If the surface of the semiconductor substrate in which the at least the plasma button is broken and/or the ash residue is in contact with the cleaning composition of the present invention, the cleaning state in the cleaning step is not In particular, it is preferred that the semiconductor substrate is impregnated into the cleaning composition of the present invention. The cleaning method of the present embodiment is preferably carried out in a state where the cleaning composition is heated in the cleaning step. The heating temperature in the washing step of the cleaning composition is not particularly limited, and is preferably 50 ° C to 90 ° C, more preferably 55 ° C to 80 ° C. Therefore, according to the present embodiment, the composition is heated and used within the above range. Therefore, it is preferred to contain a compound which does not decompose, volatilize or react at this temperature. Further, it is preferable that the pH of the composition of the temperature is not changed greatly, and the change of the cleaning composition of the above-mentioned embodiment 23 201207100 state from the room temperature to the temperature at the time of the above washing is not large and substantially Neutral. [Method of Manufacturing Semiconductor Element] Next, a preferred embodiment of the method for manufacturing a semiconductor device of the present invention will be described in detail. The method of the fourth aspect (4) includes the following steps: (a-1) side step of electrically (four) etching the semiconductor substrate, and/or (ashing step, ashing the anti-reflection on the semiconductor substrate; and (7) step by The composition is cleaned as above, and will be sprayed in the ship's engraving step tlf, and the plasmonic silver residue/disproportionation_washing formed on the material guide plate is removed. Specifically (4), preferably ^ form a via hole or The manufacturing method of the above-mentioned cleaning composition is applied to the washing material of the g& </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> The "semiconductor = substrate" in the present invention refers to the middle semiconductor in the middle of manufacturing a semiconductor element (final product). The element precursor)' is not limited to the wafer unless it is specifically limited, and includes, for example, a film or a tungsten plug, a via, a wiring, and the like. In the first embodiment, the first embodiment of the present invention is shown in FIG. 1 (0 to 3 (4) is a schematic cross-sectional view. </ br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br> The formation of Ray sβ廿, the circular domain electric solar cell and other components or 1 layer or 2 24 201207100 2 followed by the formation of the semiconductor substrate 10', the film, and the like, followed by, for example, CVD (Chemical Vapor) The PCT 1: "Chemical Rolling Deposition Method) sequentially deposits, for example, a film enamel on the entire surface, an A1 alloy film 12, for example, a titanium nitride having a film thickness of about 50 legs, and is sequentially formed into an A1 alloy film 12 and liquefied. The film of the film is formed into a conductor film. In addition, the 'A1 alloy (4) is an alloy film of A1 and Cu containing, for example, 加3 plus% to wt/o of Cu. The material is mixed with the dry method and the ship is patterned / ιό ^ The A1 alloy film 12 and the titanium nitride film 14 are formed as follows: CVD method is formed on the entire surface, for example, a film thickness ^ 5 CMp (C Hemical
Me— P〇脑ing、化學機械研磨）法，對氧化石夕膜Μ 之表面進仃研磨，使氧化賴18之表面平坦化。經過 順序，成為如圖1 (a)所示之半導體基板a。 •步驟b :參照圖1 (b) 其次’於氧化頻18上，藉由光域影法而形成 介層窗圖案之光_ R。細，將該光阻膜作為遮罩1 由電漿钱刻對氧化石夕膜18進行飯刻。此時，氧化碎膜 下之氮化欽膜14之上部亦被钱刻。由此而於氧化珍膜 上形成到達配線16之氮化鈦膜14的介層窗孔（介芦咖 案A) 20 (參照圖1⑻）。可分別使用公知之方法=圖 氧化矽膜18及氮化鈦膜14之上部的電聚钱刻。 進行 •步驟c :參照圖1 (c) 其次，藉由例如使用電漿、氧等之灰化，將用作遮罩 25 201207100 之光阻膜除去。光阻膜之灰化可使用公知之方法而進行。 於用以形成介層窗孔20之電漿蝕刻及用以除去光阻膜之 灰化中’於包含介層窗孔20周邊之表面的基板表面附著有 源自變質之光阻膜、氧化矽膜18及於介層窗孔2〇之底露 出的氮化鈦膜14之殘渣（電漿蝕刻殘渣及灰化殘渣）G。 於圖1 (c)中表示存在該殘渣G之狀態。 •步驟d :參照圖1 (d) 因此，於用以除去光阻膜之灰化後，藉由本實施形楚 之清潔組成物而對形成有介層窗孔2〇為止之半導體基相 10進行洗淨。由此而將附著於形成有介層窗孔2〇為止之 半導體基板10之表面的電漿蝕刻殘渣及灰化殘渣除去。其 結果，半導體基板d之表面成為極其清淨之狀態，成為異 有理想的電氣特性的各㈣之表面露出的狀態（參 ] ⑷）。 其次，藉由例如CVD法於整個面形成鎢膜。進一步 藉由例如CMP法，對鎢膜進行研磨直至氧化矽膜18之表 面露出。由此，於介層窗孔20内嵌入由鶴所構成之介層 窗。藉此而獲得於元件之部件界面並無上述灰化殘潰之高 品質之半導體元件。 (第2實施形態） 其次，使用圖2 (a)〜圖2 (d)對本發明之第 形態之半導體裝置的製造方法的概要加以說明丄:形 f之半導體裝置的製造方法於如下方面與第丨實施形態之 半導體裝㈣製造方法抑··形_達轉16之乂合金 26 201207100. 膜12的介層窗孔20。 •步驟a :參照圖2 (a) 首先，與第1實施形態之半導體裝置的製造方法同樣 地進行’於料體基板1〇上形成纟A1合錢12與氮化欽 膜14所構成之配線16及氧化矽膜18 (參照圖丨（約）。 •步驟b:參照圖2(b) 其次，藉由光蝕微影法，於氧化矽膜18上形成具有介 層窗圖案之光阻膜。繼而，以該光阻膜為遮罩，藉由電漿 蝕刻對氧化矽膜18及氮化鈦膜14進行蝕刻。此時，氮化 鈦膜14下之A1合金膜12之上部亦被蝕刻。由此而於氧化 矽膜18及氮化鈦膜14上形成到達配線16之A1合金膜 的"層έι孔2G (介層窗圖案b)。可分別使用常法而進行 氧化矽膜18、氮化鈦膜14及A1合金膜12之上部 侧。 浆 •步驟c :參照圖2 (c) 其次，藉由例如使用電漿、氧等之灰化，將用作遮罩 之光阻膜除去。光_之灰化可使用公知之方法而進行。 於本實施賴之情料，闕⑽敍層窗孔如之乾式钮 刻及用以除去光阻膜之灰化中，於包含介層窗孔2〇周邊之 表面及介層窗孔20之壁面的基板表面附著有f漿飯刻殘 渣及灰化紐。於本形態之情科，電祕刻殘渣及 灰化殘漬不健源自變質之光_、氧化销18及氮化欽 膜14’而且亦源自於介層窗孔20底所露出之A1合金膜12。 •步驟d :參照圖2 (d) 、 27 201207100 因此，於用以除去光阻膜之灰化後，藉由本實施形態 之清潔組成物對形成有介層窗孔20為止之半導體基板1〇 進行洗淨。由此而將附著於形成有介層窗孔2〇為止之半導 體基板10之表面的電漿蝕刻殘渣及灰化殘渣除去。其結 果，半導體基板d之表面成為極其清淨之狀態，成為具有 理想之電氣特性的各材料之表面露出的狀態。於本實施形 態中，特別是與介層窗孔之底部接觸之鋁（A1)合金膜12 之表面亦被充分地洗淨而露出其清淨面。 其次，與第1實施形態之半導體裝置的製造方法同樣 地，仃而形成嵌入至介層窗孔2〇内之介層窗。藉此而獲得 於tl件之部件界面並無上述灰化殘渣之高品質之半導體元 件。 (第3實施形態） ^其次，使用圖3 (a)〜圖3 (d)對本發明之第3實施 形態之半導體裝置的製造方法的概要加以說明。 •步驟（a):參照圖3 (a) 首先，與第1實施形態之半導體裝置的製造方法同樣 地進行，於形成有元件等之半導體基板上，形成層間絕緣 膜（氧化石夕膜）24。其次，藉由例如CVD法，於整個面 順次積層例如膜厚約5Q nm之氮化鈦膜26、例如膜厚約 2〇 nm之鈦膜28、例如膜厚約500 nm之A1合金膜30、例 如膜厚約50 nm之氮化鈦膜32。另外，A1合金膜3〇是例 如含有0,1%〜5%之Cu的A1與Cu之合金膜。上述尺寸僅 為-例’本實施轉並稀解釋為限定於此。 28 201207100. •步驟b :參照圖3 (b) 其次，於氮化鈦膜32上，藉由光蝕微影法而形成具有 配線圖案之光阻膜。繼而，將該光阻膜作為遮罩，藉由電 漿蝕刻依序對氮化鈦膜32、A1合金膜30、鈦膜28 i氮化 鈦膜26進行蝕刻。由此而對氮化鈦膜32、A1合金膜3〇、 鈦膜28及氮化鈦膜26進行圖案化，形成由該些導體膜所 構成之配線（配線圖案）34。 、 •步驟c :參照圖3 (c) 其次，藉由使用化學藥品之濕式處理，將用作遮罩之 光阻膜之大部分剝離除去。繼而，藉由例如使用電漿、氧 等之灰化，將光阻膜之剩餘部分除去（參照圖3 (c))。於 用以形成配線34之電漿蝕刻及用以除去光阻膜之剩餘部 分的灰化中，如圖3 (c)所示那樣，於包含配線34之上 表面及侧面之基板表面附著有殘渣（電漿蝕刻殘渣及灰化 殘渣）G。該殘渣G源自變質之光阻膜、氮化鈦膜32、μ 合金膜30、鈦膜28及氮化鈦膜26。 •步驟d :參照圖3 (d) 因此，於用以除去光阻膜之剩餘部分的灰化後，藉由 本發明之清潔組成物，對形成有配線3 4為止之半導體^板 1〇進行洗淨。由此而將附著於形成有配線34為止之^導 體基板10之表面的電漿姓刻殘逢及灰化殘潰除去。1社 果，半導體基板d之表面成為極其清淨之狀態，成為^ 理想的電氣特性的各材料之表面露出之狀g (參照圖、3 ⑷）。特別是藉由本實施形態，可防止凹槽（源極與沒極 29 201207100 之間的溝）29中之金屬腐姓而較佳。 另外，於上述實施形態中，對形成包含A1合金膜12、 30之配線16、34之情形加以說明，但配線之材料並不限 定於上述材料。作為配線，除了由A1或A1合金所構成之 以A1為主材料之配線以外，亦可形成由Cu或Cu合金所 構成之以Cu為主材料之配線。 而且，本發明之清潔組成物可廣泛用於自包含鋁或銅 之半導體基板洗淨電漿蝕刻殘渣及/或灰化殘渣的步驟 中，較佳的是於在半導體用基板上所形成之配線結構中包 含鋁或銅。如上所述，於各種各樣之形態及條件的半導體 製造步驟中’本實施形態之清潔液起職果，經由利用該 /月泳液之洗淨而製造的半導體元件之部件界面並無上述殘 渣，可獲得品質極其高之半導體元件。 [實例] 以下，藉由實例對本發明加以更詳細之說明。但是本 發明並不限定於該些實例。 <實例、比較例> 使以下表1中所示之成分，以同一表中所示之組成 (Wt%)而含有於水中，調製清潔組成物1G1〜清潔組成 物115之液體（實例）。水使用於半導體製造步驟中所使用 之了般的超純水。而且，相對於上述實例，如表！所示那 樣變更成分組成，調製清潔組成物eU、清潔組成物⑴ (比較例）、清潔組成物sll、清潔組成物sl2 (參考例） 之液體H以表中之量而含有於表中表示組成（wt%) 201207100 之成分’以成為關於各試樣而表示之pH的量而含有驗性 有機化合物。於該些中’表示包含水之組成（wt%)合計 成為lOOwt%。表中之pH是於室溫⑵^)下藉由H〇RiBA 公司製造之F-51 (商品名）而測定之值。 <洗淨試驗> _於上述帛1實卿態及帛2實施形態，於形成介層 窗孔後’藉由掃描電子顯微鏡（SEM : s_ing mectr〇nMe-P camphor ing, chemical mechanical polishing method, the surface of the oxidized stone enamel is ground and polished to flatten the surface of the oxidized ray 18 . After the order, the semiconductor substrate a shown in Fig. 1(a) is obtained. • Step b: Referring to Fig. 1 (b), the light _ R of the via pattern is formed by the optical domain method on the oxidation frequency 18. Finely, the photoresist film is used as a mask 1 to engrave the oxidized stone film 18 by plasma. At this time, the upper part of the nitride film 14 under the oxidized film is also engraved. Thereby, a via hole (Mei A A) 20 which reaches the titanium nitride film 14 of the wiring 16 is formed on the oxide film (see Fig. 1 (8)). A well-known method = a graph of the ruthenium oxide film 18 and the upper portion of the titanium nitride film 14 can be used. Performing • Step c: Referring to Fig. 1 (c) Next, the photoresist film used as the mask 25 201207100 is removed by, for example, ashing using plasma, oxygen, or the like. Ashing of the photoresist film can be carried out by a known method. In the plasma etching for forming the via hole 20 and the ashing for removing the photoresist film, a photoresist film derived from deterioration and yttrium oxide are attached to the surface of the substrate including the surface around the via hole 20 The film 18 and the residue (plasma etching residue and ashing residue) G of the titanium nitride film 14 exposed at the bottom of the via hole 2〇. The state in which the residue G exists is shown in Fig. 1 (c). • Step d: Referring to FIG. 1(d), after the ashing for removing the photoresist film, the semiconductor base phase 10 formed with the via hole 2 is formed by the cleaning composition of the present embodiment. Wash. Thereby, the plasma etching residue and the ashing residue adhering to the surface of the semiconductor substrate 10 on which the via hole 2 is formed are removed. As a result, the surface of the semiconductor substrate d is extremely clean, and the surface of each (4) having an excellent electrical characteristic is exposed (see (4)). Next, a tungsten film is formed on the entire surface by, for example, a CVD method. Further, the tungsten film is polished by, for example, a CMP method until the surface of the yttrium oxide film 18 is exposed. Thereby, a via window composed of cranes is embedded in the via hole 20. As a result, a high-quality semiconductor element having no such ashing residue is obtained at the interface of the component. (Second Embodiment) Next, an outline of a method of manufacturing a semiconductor device according to a first aspect of the present invention will be described with reference to FIGS. 2(a) to 2(d). A method of manufacturing a semiconductor device of the form f is as follows.半导体 Semiconductor package of the embodiment (4) Manufacturing method ·························· (Step a) Referring to Fig. 2 (a) First, in the same manner as the method of manufacturing the semiconductor device of the first embodiment, the wiring formed by forming the 纟A1 coin 12 and the nitriding film 14 on the material substrate 1 is performed. 16 and yttrium oxide film 18 (refer to Fig. 约 (about). • Step b: refer to Fig. 2 (b). Next, a photoresist film having a via pattern is formed on the yttrium oxide film 18 by photolithography. Then, the ruthenium oxide film 18 and the titanium nitride film 14 are etched by plasma etching using the photoresist film as a mask. At this time, the upper portion of the A1 alloy film 12 under the titanium nitride film 14 is also etched. Thus, the "layer έ hole 2G (via window pattern b) of the A1 alloy film reaching the wiring 16 is formed on the yttrium oxide film 18 and the titanium nitride film 14. The yttrium oxide film 18 can be separately formed by a usual method. The titanium nitride film 14 and the upper portion of the A1 alloy film 12. Pulp • Step c: Referring to Fig. 2 (c) Next, a photoresist film used as a mask is used by, for example, ashing using plasma, oxygen, or the like. The ashing of the light can be carried out by a known method. In the case of the present embodiment, the 阙(10) layered window hole is as dry button and used to remove the photoresist. In the ashing, the surface of the substrate including the surface of the via hole 2〇 and the wall surface of the via hole 20 are adhered with a residue of the pulverized rice residue and the ashing ruth. In the case of this form, the electric secret residue And the ashing residue is not derived from the metamorphic light _, the oxidized pin 18 and the nitriding film 14' but also originates from the A1 alloy film 12 exposed at the bottom of the via hole 20. • Step d: Refer to FIG. (d), 27 201207100 Therefore, after the ashing for removing the photoresist film, the semiconductor substrate 1A having the via hole 20 formed thereon is cleaned by the cleaning composition of the present embodiment. The plasma etching residue and the ashing residue adhering to the surface of the semiconductor substrate 10 on which the via hole 2 is formed are removed. As a result, the surface of the semiconductor substrate d is extremely clean, and each has excellent electrical characteristics. In the present embodiment, in particular, the surface of the aluminum (A1) alloy film 12 which is in contact with the bottom of the via hole is sufficiently washed to expose the clean surface. The manufacturing method of the semiconductor device of the embodiment is the same Further, a via window is formed which is embedded in the via hole 2, thereby obtaining a high-quality semiconductor element having no ash residue as described in the component interface of the tl device. (Third embodiment) ^Second An outline of a method of manufacturing a semiconductor device according to a third embodiment of the present invention will be described with reference to Fig. 3 (a) to Fig. 3 (d). Step (a): Refer to Fig. 3 (a) First, the first embodiment In the same manner as in the method of manufacturing a semiconductor device, an interlayer insulating film (oxidized oxide film) 24 is formed on a semiconductor substrate on which a device or the like is formed. Next, for example, a film thickness of about 5 Q is sequentially formed over the entire surface by, for example, a CVD method. The titanium nitride film 26 of nm, for example, a titanium film 28 having a film thickness of about 2 Å, for example, an A1 alloy film 30 having a film thickness of about 500 nm, for example, a titanium nitride film 32 having a film thickness of about 50 nm. Further, the A1 alloy film 3 is, for example, an alloy film of A1 and Cu containing 0, 1% to 5% of Cu. The above dimensions are merely examples - and the present embodiment is to be construed as being limited thereto. 28 201207100. • Step b: Referring to Fig. 3 (b) Next, a photoresist film having a wiring pattern is formed on the titanium nitride film 32 by photolithography. Then, the photoresist film is used as a mask, and the titanium nitride film 32, the Al alloy film 30, and the titanium film 28 i titanium nitride film 26 are sequentially etched by plasma etching. Thereby, the titanium nitride film 32, the A1 alloy film 3A, the titanium film 28, and the titanium nitride film 26 are patterned to form wirings (wiring patterns) 34 composed of the conductor films. • Step c: Referring to Fig. 3 (c) Next, most of the photoresist film used as a mask is peeled off by wet processing using a chemical. Then, the remaining portion of the photoresist film is removed by, for example, ashing using plasma, oxygen or the like (refer to Fig. 3 (c)). In the ash etching for forming the wiring 34 and the ashing for removing the remaining portion of the photoresist film, as shown in FIG. 3(c), the residue adheres to the surface of the substrate including the upper surface and the side surface of the wiring 34. (plasma etching residue and ashing residue) G. This residue G is derived from a deteriorated photoresist film, a titanium nitride film 32, a μ alloy film 30, a titanium film 28, and a titanium nitride film 26. • Step d: Referring to FIG. 3(d), after the ashing for removing the remaining portion of the photoresist film, the semiconductor device 1 形成 formed with the wiring 34 is washed by the cleaning composition of the present invention. net. As a result, the plasma adhering to the surface of the conductor substrate 10 on which the wiring 34 is formed is removed and removed by ashing. As a result, the surface of the semiconductor substrate d is extremely clean, and the surface of each material which is an ideal electrical property is exposed (see Fig. 3, (4)). In particular, according to the present embodiment, it is preferable to prevent the metal rot in the groove (the groove between the source and the gate 29 201207100) 29. Further, in the above embodiment, the case where the wirings 16 and 34 including the A1 alloy films 12 and 30 are formed will be described, but the material of the wiring is not limited to the above materials. As the wiring, in addition to the wiring made of A1 or the A1 alloy and mainly composed of A1, a wiring made of Cu or a Cu alloy and mainly composed of Cu may be formed. Further, the cleaning composition of the present invention can be widely used in a step of cleaning a plasma etching residue and/or an ash residue from a semiconductor substrate containing aluminum or copper, preferably a wiring formed on a substrate for a semiconductor. The structure contains aluminum or copper. As described above, in the semiconductor manufacturing process of various forms and conditions, the cleaning liquid of the present embodiment has a result that the component interface of the semiconductor element manufactured by the cleaning using the liquid of the moon liquid does not have the residue. A semiconductor component of extremely high quality can be obtained. [Examples] Hereinafter, the present invention will be described in more detail by way of examples. However, the invention is not limited to the examples. <Examples, Comparative Examples> The components shown in the following Table 1 were contained in water in the composition shown in the same table (Wt%) to prepare a liquid for cleaning the composition 1G1 to the cleaning composition 115 (example) . Water is used for ultrapure water as used in semiconductor manufacturing steps. Moreover, as opposed to the above examples, such as the table! The composition of the composition is changed as shown, and the liquid composition H of the cleaning composition eU, the cleaning composition (1) (comparative example), the cleaning composition s11, and the cleaning composition sl2 (reference example) is contained in the table and expressed in the table. (wt%) The component '201207100' contains an organic compound in an amount to be the pH expressed for each sample. In the above, 'the composition (wt%) containing water is a total of 100% by weight. The pH in the table is a value measured by F-51 (trade name) manufactured by H〇RiBA Co., Ltd. at room temperature (2)^). <washing test> _ in the above-mentioned 帛1 real state and 帛2 embodiment, after forming a via hole' by scanning electron microscopy (SEM: s_ing mectr〇n
Microscope)對圖案晶圓進行觀察，結果均於介層窗孔壁 面上確認電漿蝕刻殘渣及灰化殘渣（參照圖丨（c)及圖2 (Ο)。而且，關於上述第3實施形態，於形成配線後，藉 由SEM 案晶圓進行觀察，結果於配線之上表面及側 面確認電漿蝕刻殘渣及灰化殘渣（參照圖3 (c))。 於將溫度調節為表1中所記載之溫度的上述各清潔組 成物中，浸潰附著有上述殘渣之圖案晶圓之切片（約2 cmx2 cm)，從表1中所記載之上述各清潔組成物中取出圖 案晶圓切片，立即以超純水加以水洗，進行n2乾燥。藉由 SEM觀察浸潰試驗後之圖案晶圓切片之剖面及表面，依照 下述之判斷基準對光阻劑及殘渣（電漿蝕刻殘渣及灰化殘 渣）之除去性、以及A1及TiN之腐餘性進行評價。將除 去性及腐银性之評價結果記載於表1中。 〈介詹窗孔周邊之表面的殘渣除去> AA :光阻劑及殘渣被完全除去。 A:光阻劑及殘渣基本上被完全除去。 B :殘存有光阻劑及殘渣之溶解不良物。 31 201207100 c:光阻劑及殘渣基本上未被除去。 <介層窗孔底之金屬層之腐蝕> AA :未發現TiN之腐蝕。 A : TiN之腐蝕相對於配線而言為5%以下。 B : TiN之腐蝕相對於配線而言為10%以下。 C : TiN完全消失。 <介層窗孔底之矽層之腐蝕> AA :未發現碎之腐餘。 A :矽之腐蝕相對於配線而言為5%以下。 B :矽之腐蝕相對於配線而言為10%以下。 C:矽完全消失。 另外，關於第3實施形態，並非對介層窗孔周邊之表 面，而是對配線側面、上表面之殘渣除去的狀態進行觀察 評價。而且，關於金屬層，藉由A1腐蝕（凹槽）而進行評 價。評價基準與上述同樣。 [表1] 32 201207100 $ % 5 < i % $ < $ % % % % %When the pattern wafer was observed, the plasma etching residue and the ash residue were confirmed on the wall surface of the via window (see FIG. 丨 (c) and FIG. 2 (Ο). Further, regarding the third embodiment, After the wiring was formed, the SEM wafer was observed, and the plasma etching residue and the ash residue were confirmed on the upper surface and the side surface of the wiring (see FIG. 3(c)). The temperature was adjusted as shown in Table 1. In each of the above-mentioned cleaning compositions at a temperature, a slice (about 2 cm x 2 cm) of the pattern wafer to which the residue adhered was impregnated, and the pattern wafer slice was taken out from each of the cleaning compositions described in Table 1, and immediately The ultrapure water was washed with water and dried by n2. The cross section and surface of the pattern wafer slice after the impregnation test were observed by SEM, and the photoresist and the residue (plasma etching residue and ash residue) were determined according to the following criteria. The removability and the residual property of A1 and TiN were evaluated. The evaluation results of the removability and rosin resistance are shown in Table 1. <Residue removal on the surface around the window hole> AA: Photoresist and The residue was completely removed. A: Photoresist And the residue is almost completely removed. B: Residual dissolved matter of photoresist and residue remains. 31 201207100 c: The photoresist and the residue are not substantially removed. <Corrosion of the metal layer at the bottom of the via hole> AA: No corrosion of TiN was observed. A: Corrosion of TiN is 5% or less with respect to wiring. B: Corrosion of TiN is 10% or less with respect to wiring. C : TiN disappears completely. < Corrosion of the layer of the bottom of the hole> AA: No residue was found. A: The corrosion of the crucible was 5% or less with respect to the wiring. B: The corrosion of the crucible was 10% or less with respect to the wiring. In addition, in the third embodiment, the state in which the residue on the side surface and the upper surface of the wiring is removed is not observed on the surface around the via hole, and the metal layer is corroded by A1 ( The evaluation was performed in the same manner as above. [Table 1] 32 201207100 $ % 5 < i % $ < $ % % % % %
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MU s2 gt 51 °32 601 0- 5 -s 33 201207100 表中之簡稱表示如下所示之内容。 •「％」表示wt%。 (清潔劑） • HAS:羥胺硫酸鹽 • HA :羥胺 • FA :氟化銨 • CAM :胺曱酸曱酯 (鹼性有機化合物） • TMAH :氫氧化四曱基銨 • EDA :乙二胺 (高分子化合物） • PVP :聚乙稀1»比洛咬酉同 • PVA :聚乙烯醇 • PA A :聚丙稀酸 (含胺基之羧酸） AG :精胺酸 (有機溶劑）MU s2 gt 51 °32 601 0- 5 -s 33 201207100 The abbreviation in the table indicates the contents as shown below. • "%" means wt%. (Cleanser) • HAS: Hydroxylamine sulfate • HA: Hydroxylamine • FA: Ammonium fluoride • CAM: Ammonium decanoate (alkaline organic compound) • TMAH: Tetramethylammonium hydroxide • EDA: Ethylenediamine ( Polymer compound) • PVP: Polyethylene 1»Bilo bite • PVA: Polyvinyl alcohol • PA A : Polyacrylic acid (amino acid-containing carboxylic acid) AG : Arginine (organic solvent)
BuDO : 1，3-丁二醇 DPG :二丙二醇 (酸性有機化合物） A A :乙酸 CA :檸檬酸 GA :乙醇酸 GLA :葡萄糖酸 34 201207100 LA :乳酸 ΜΑ :蘋果酸 ML A .馬來酸 ΜΝΑ :丙二酸 OA :草酸 PA :丙酸 SUA :琥珀酸 TA :酒石酸 DGA :氧二乙酸 FOA :曱酸 •殘渣除去[1]··對 表面之殘渣除去的評價^第1實施形態之介層窗孔周邊之 •金屬腐蝕[1]··對二果 aBuDO: 1,3-butanediol DPG: dipropylene glycol (acidic organic compound) AA: acetic acid CA: citric acid GA: glycolic acid GLA: gluconic acid 34 201207100 LA: lactic acid bismuth: malic acid ML A. maleic acid hydrazine: Malonic acid OA: oxalic acid PA: propionic acid SUA: succinic acid TA: tartaric acid DGA: oxydiacetic acid FOA: citric acid, residue removal [1] · Evaluation of residue removal on the surface ^ The first embodiment of the via window Metal corrosion around the hole [1]··对二果 a
之腐蝕的評價結果 實施形態之介層窗孔底之TiN 實施形態之介層窗孔底之矽之 • Si腐蝕[1]:對於第 腐蝕的評價結果 殘/查除去[2] ·對於第2實施形態之介層窗孔周邊之 表面之殘〉查除去的評價結果 •金屬腐钱[2]:對於第2實施形態之介層窗孔底之 A1之腐蝕的評價結果 • Si腐餘[2]:對於第2實施形態之介層窗孔底之矽之 腐蝕的評價結果 •殘渣除去[3]:對於第3實施形態之配線侧面、上表 面之殘渣除去的評價結果 35 201207100 •金屬腐钱[3]:第3實施形態之A1之腐蝕（凹槽） 中的評價結果 • Si腐触[3]··對於第3實施形態之凹槽之矽之腐蝕的 評價結果 如上述表1所示，可知本發明之清潔組成物（實例） 於各種各樣之形態的半導體元件之製造中，防止半導體基 板之金屬部件及矽之腐蝕，且可充分除去於其製造步驟中 所產生之電漿蝕刻殘渣或灰化殘渣。特別是相對於為酸性 且不含间分子化合物之組成物（比較例）而言，顯示出極 其尚的洗淨力與金屬之腐蝕防止效果。於氟化銨或羥胺與 聚乙烯吡咯啶酮組合而成之清潔液（比較例 :相當於曰本 專利3891768號說明書之實例！、實例⑴中，金屬或石夕 之防蝕性差。而且’相對於為中性但並未使用高分子化合 物之組成物（參考例）而言，金屬之腐蝕防止效果高（對 比參照組成物103〜組成物1〇5、組成物sU、組成物si2)。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 =範圍内，當可作些許之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 圖1 U)〜圖1 (d)是對表示本發明之清潔組成物之 使用中的-實施祕的半導體元件之製造步驟之—部分加 以概略性表示的步驟說明圖。 圖2 (a)〜圖2 (d)是對表示本發明之清潔組成物之 36 201207100 使用中的其他實施態樣的半導體元件之製造步驟之一部分 加以概略性表示的步驟說明圖。 圖3(a)〜圖3(d)是對表示本發明之清潔組成物之 使用中的另一其他實施態樣的半導體元件之製造步驟之一 部分加以概略性表示的步驟說明圖。 【主要元件符號說明】 10 :半導體基板 12:A1合金膜 14、26、32 :氮化鈦膜 16 :配線 18 :氧化矽膜 20 :介層窗孔（介層窗圖案A) / (介層窗圖案B) 24 :層間絕緣膜（氧化矽膜） 28 :鈦膜 29:凹槽（源極與汲極之間的溝） .30:A1合金膜 34 :配線（配線圖案） G:殘澄（電漿#刻殘渣及灰化殘渣） R :光阻膜 37Corrosion evaluation results TiN of the via hole at the bottom of the embodiment window. Si etching [1]: Evaluation of the first corrosion residue/check removal [2] · For the second Evaluation result of the surface of the periphery of the via hole of the embodiment, and the result of the evaluation of the metal corrosion (2): Evaluation result of the corrosion of the A1 of the via hole at the bottom of the second embodiment window • Si rot remaining [2] [Evaluation result of the corrosion of the enthalpy of the via hole in the second embodiment] Residue removal [3]: Evaluation result of the removal of the residue on the side surface and the upper surface of the wiring of the third embodiment 35 201207100 • Metal rot [3]: Evaluation results in the corrosion (groove) of A1 of the third embodiment. • Si rot [3]·· The evaluation results of the corrosion of the groove of the third embodiment are as shown in Table 1 above. It is understood that the cleaning composition (example) of the present invention prevents the corrosion of the metal member and the crucible of the semiconductor substrate in the manufacture of various types of semiconductor elements, and can sufficiently remove the plasma etching generated in the manufacturing steps thereof. Residue or ash residue. In particular, it exhibits an extremely excellent detergency and a metal corrosion preventing effect with respect to a composition which is acidic and does not contain a molecular compound (comparative example). A cleaning solution prepared by combining ammonium fluoride or hydroxylamine with polyvinylpyrrolidone (Comparative Example: equivalent to the example of the specification of the patent No. 3891768!, in the example (1), the metal or the stone has poor corrosion resistance. The composition which is neutral but does not use a polymer compound (reference example) has a high corrosion prevention effect of the metal (comparative reference composition 103 to composition 1〇5, composition sU, composition si2). The invention has been disclosed in the above preferred embodiments, but it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope is defined by the scope of the appended patent application. [Simplified illustration of the drawings] Fig. 1 U) to Fig. 1 (d) are semiconductor elements for the implementation of the cleaning composition of the present invention. The steps of the manufacturing steps are partially explained in outline. Fig. 2 (a) to Fig. 2 (d) are explanatory diagrams schematically showing a part of the manufacturing steps of the semiconductor element of another embodiment in which the cleaning composition of the present invention is used in the 201207100. Fig. 3 (a) to Fig. 3 (d) are explanatory diagrams schematically showing a part of the manufacturing steps of the semiconductor element showing still another embodiment of the cleaning composition of the present invention. [Description of main components] 10: Semiconductor substrate 12: A1 alloy film 14, 26, 32: Titanium nitride film 16: Wiring 18: Cerium oxide film 20: via hole (via window pattern A) / (interlayer Window pattern B) 24: interlayer insulating film (yttria film) 28: titanium film 29: groove (groove between source and drain) . 30: A1 alloy film 34: wiring (wiring pattern) G: (plasma #刻 residue and ash residue) R: photoresist film 37
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| KR102573354B1 (en) | 2013-12-06 | 2023-08-30 | 후지필름 일렉트로닉 머티리얼스 유.에스.에이., 아이엔씨. | Cleaning formulation for removing residues on surfaces |
| KR102434147B1 (en) * | 2016-10-06 | 2022-08-19 | 후지필름 일렉트로닉 머티리얼스 유.에스.에이., 아이엔씨. | Cleaning formulations for removing residues on semiconductor substrates |
| JP7122258B2 (en) * | 2017-01-17 | 2022-08-19 | 株式会社ダイセル | Semiconductor substrate cleaner |
| JP6962247B2 (en) | 2018-03-14 | 2021-11-05 | Jsr株式会社 | Semiconductor surface treatment composition and semiconductor surface treatment method |
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| JP3891768B2 (en) * | 1999-12-28 | 2007-03-14 | 株式会社トクヤマ | Residual cleaning solution |
| JP2003297790A (en) * | 2002-04-04 | 2003-10-17 | Mitsubishi Gas Chem Co Inc | Treatment liquid and treatment method of semiconductor substrate |
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