4268 1 6 A7 B7 經濟部中央樣準局貝工消费合作杜印袈 五、發明説明（1 ) 本發明之起源 本發明爲1 9 9 3年6月2 1日所申請之申請書系列 號碼0 8/0 7 8 6 5 7之部份連續申請案（其爲 1 9 9 2年7月9日所申請之申請書系列號碼0 7/9 1 1 1 0 2之部份連續申請案*現今爲美國專利5，3. 3 4 ’332)，而07/911102爲在1990年11 月5曰所申請之申請書系列號碼07/610044之部 份連續申請案（現今爲美國專利5，279，771) · 這些申請書之發明在本申請書中合併列爲參考。 本發明之背景 1 .發明之頜域 本發明大概係關於一種從受質上移除聚合物質與有機 ，有機金屬及金屬氧化物剩餘物之剝離與洗滌組合物及方 法。尤其是關於在積體電路與相似程序之製造中在電漿蝕 刻程序之後，用以移除聚合物，例如光阻材料，聚醯亞胺 ，與其類似物及蝕刻剩餘物之組合物與方法。最特別的是 關於此類組合物與方法有效地移除這些材料，避免其侵蝕 在積體電路中所採用之金屬層，包括鈦層》 2 .先前技藝之描沭 至於在矽或其他半導體晶片上積體電路製造變成相當 複雜，因此所製造之電路元件之大小變成較小•用以移除 光阻材料或其他聚合物質及從此類物質上所形成之剩餘物 (請先閲讀背面之注項再填寫本頁) ,11 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 4 - 4 268 1 6 A7 B7 五、發明説明（2 ) 之技術連續改良是需要的。光阻材料或其他聚合物質’例 如聚醯亞胺，在受質中所定義之圖案製造程序期間通常遭 受離子插入，電漿蝕刻，活性離子蝕刻或離子銑削。此外 *氧電漿氧化作用通常用於移除光阻材料或其他聚合物質 ，在其使用之後，製造程序完成之。此類高能量方法典型 上導致在製造過程中所形成之結構側壁上光阻材料之硬化 及有機金屬與其他剩餘物之形成。 一般在積體電路製造中所採用者爲不同之金屬與其他 層，包括鋁，鋁/矽/銅，鈦，氮化鈦，鈦/鎢，鯓，氧 化矽，聚矽結晶體與其他類似物。此類不同層之使用導致 在高能量過程中不同之有機金靥剩餘物之形成β除了用於 移除光阻材料或其他聚合物質或剩餘物有效之外，剝離與 洗滌組合物在積體電路製造中使用，亦不會侵蝕不同之冶 金。 (請先閱讀背面之注意事項再填寫本頁) --5 經濟部中央橾举局負工消費合作社印製4268 1 6 A7 B7 Duyin 贝, Cooperating with Shelling Consumers of the Central Sample Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Origin of the invention The invention is the serial number of the application filed on June 21, 1993 8/0 7 8 6 5 7 part of the continuous application (which is the serial number of the application filed on July 9, 1982 0 7/9 1 1 1 0 2 part of the continuous application * now U.S. Patent 5, 3. 3 4 '332), and 07/911102 is part of a serial application for application serial number 07/610044, which was filed on November 5, 1990 (now U.S. Patent 5,279, 771) The inventions of these applications are incorporated herein by reference. BACKGROUND OF THE INVENTION 1. The Jaw Field of the Invention The present invention is generally related to a stripping and washing composition and method for removing polymeric substances and organic, organometallic and metal oxide residues from a substrate. In particular, it relates to compositions and methods for removing polymers, such as photoresist materials, polyimide, and the like, and etching residues after the plasma etching process in the manufacture of integrated circuits and similar processes. The most special thing is that these compositions and methods effectively remove these materials and prevent them from eroding the metal layers used in integrated circuits, including titanium layers. 2. The description of previous techniques for silicon or other semiconductor wafers The manufacturing of the upper integrated circuit has become quite complicated, so the size of the circuit components manufactured has become smaller. • To remove photoresist materials or other polymer materials and the residue formed from such materials (please read the note on the back first) (Fill in this page again), 11 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) _ 4-4 268 1 6 A7 B7 V. Technical description of the invention (2) Continuous improvement is needed. Photoresist materials or other polymeric materials, such as polyimide, are typically subjected to ion insertion, plasma etching, reactive ion etching, or ion milling during the patterning process defined in the substrate. In addition, oxygen plasma oxidation is usually used to remove photoresist materials or other polymer materials. After its use, the manufacturing process is completed. Such high-energy methods typically result in the hardening of photoresist materials and the formation of organometals and other residues on the sidewalls of structures formed during the manufacturing process. Generally used in the manufacture of integrated circuits are different metals and other layers, including aluminum, aluminum / silicon / copper, titanium, titanium nitride, titanium / tungsten, hafnium, silicon oxide, polysilicon crystals, and other similar materials. The use of such different layers results in the formation of different organic gold tincture residues in the high-energy process. In addition to being effective for removing photoresist materials or other polymeric substances or residues, the stripping and washing composition is used in integrated circuits. Used in manufacturing, it will not erode different metallurgy. (Please read the precautions on the back before filling out this page) --5 Printed by the Consumer Affairs Cooperative of the Central Government Bureau of the Ministry of Economic Affairs
本發明之摘要 以羥胺爲基礎之組合物，如在上述所參考之先前申請 書與已發佈之專利所描述，這些組合物可從E K C技術公 司購得，本發明之受託者曾證明非常有效地用於積體電路 工業中光阻材料與蝕刻剩餘物之移除公式。在積體電路工 業中，由於連續努力降低關鍵性之尺寸大小•例如在微米 大小之下之元件製造，在濕加工程序中所採用之與化學藥 品適合性之受質與蝕刻剩餘物之移除用以在非常大規模之 積體電路（VLS I )與過度大規模積體電路（ULS I 蟓 本紙張尺度通用中國國家標準（CNS ) A4洗格（2丨0X297公釐） 4 268 1 6 A7 _B7_ 五、發明説明（3 ) )程序中獲得可接受之產率變成非常非常之關鍵性。此類 蝕刻剩餘物之組合物通常係由經蝕刻之受質’基礎之受質 ，光阻材料與蝕刻氣體所構成。晶片與濕化學藥品之受質 適合性，例如與羥胺組合物之適合性，是高度視聚矽，在 薄膜鍍層中多層級互連介電層與金饜噴鍍，晶片之蝕刻與 後蝕刻處理而定，通常從一種製造方法換成另一種製造方 法通常是相當不同的。 在一些環境中，羥胺組合物，例如包含兒苯酚（1， 2 —二羥基苯）之組合物•在某些金靥受質上產生腐蝕性 ，例如在包括鈦金靥層之金屬受質或包括鋁層之受質在高 溫，意即超過6 5 °C產生腐蝕》在半導體製造過程中欽已 廣泛地使用。採用二者做爲阻擋層而避免某些原子之電子 移動及做爲在其他金屬頂端之抗反射層。在可適用之美國 聯邦政府之條例（S E RA標題Ε)之下，兒苯酚被認爲 是一種危害物質。在半導體工業，爲了推動導入更有效率 與較少毒性之化學藥品產物，進行研究而發現在羥胺組合 物中適合取代兒苯酚之產物。 經濟部中央標隼局員工消費合作社印製 (請先閲讀背面之注$項再填寫本！) 所以，本發明之目的爲提供一種經改良之以羥胺爲基 _礎之組合物及使用此類組合物以適合符合目前半導體製造 要求之方法β 本發明之另一目的爲提供一種適合從晶片與其他包括 ~或多鈦金屬層之受質上移除光阻材料與其他聚合物質與 剩餘物而不會侵蝕此類鈦層之組合物與方法。 本發明更進一步之目的爲提供一種包含更健康且不會 本紙張尺度適用中國國家樣準（CNS ) Α4規格（210Χ297公釐} -6 - 經濟部中央標準局貝工消費合作杜印製 426816 A7 ___B7_五、發明説明（4 ) 對環境造成污染之化學藥品之組成物與方法。 這些成就與相關之目的可經由取用在此所發明之羥胺 一五倍子酸化合物組合物與方法而達成》根據本發明之羥 胺一五倍子酸化合物組合物包含羥胺化合物，至少一可與 羥胺化合物溶混之醇胺化合物與五倍子酸化合物*根據本 發明從受質上移除光阻材料或其他聚合物質或剩餘物之方 法包括在足夠從受質上移除光阻材料，其他聚合物質或剩 餘物之溫度，將受質與羥胺化合物，可與羥胺化合物溶混 之醇胺化合物及五倍子酸化合物接觸一段時間》 實際上，發現以近乎等量之五倍子酸化合物取代兒苯 酚而用於移除剩餘物或剝離與洗滌光阻材料，其侵蝕鈦之 程度至少約小於包含兒苯酚組成物侵蝕程度之3倍。然而 ，包括五倍子酸化合物組合物得到做爲移除剩餘物或剝離 與洗滌光阻材料之組合物之相同性能。 本發明先前所述之成就與相關目的，利益與特徵在回 顧下列本發明更詳細之描述與圖形之後，對熟知此技藝之 人士將是顯而易知的。 圖彤之簡要描述 圖1 - 4爲顯示在以另一剝離與洗滌及移除剩餘物之 組合物處理之後與根據本發明之剝離與洗滌及移除剩餘物 之組合物處理之後在鈦厚度量測之比較結果之圖形。 圖5 A — 1 4 B爲顯示使用本發明之組合物與方法所 達到之比較結果之掃描式電子顯微鏡（S EM)照片。 本紙張尺度通用中國國家標隼（CNS ) A4規格（2lOX25>7公釐) (請先閣讀背面之注意事項再填寫本頁) 訂 41 一 7 - 經濟部中央榡準局員工消费合作杜印製 4 2 6 8 16 A7 _____B7 _五、發明説明（5 ) 本發明之詳細描述 適合用於本發明之羥胺具有結構式H2N — Ο Η。羥 胺在很多方法中所具有之特性在於聯胺，Η2Ν — ΝΗ2 ，與過氧化氫，HO -OH之間，依照其可建議之化學式 而展現。在純態羥胺爲一種具有熔點3 3 °C之無色溶解之 固體，其在加熱時起曝並緩慢地分解，在週遭溫度或室溫 引出氮與氧化亞氮*羥胺可從倪信（Nissin )化學公司 商業上以約5 0重量％在水中之水溶液購得。倪信化學公 司將適當之安定劑加入此溶液中而改善其儲放安定性。實 際上，在本發明中採用此羥胺之商業上可購買到之形式與 參考商業上可購買到之形式之詳述量。由製造商所記錄之 報告，羥胺與鈦是不相容的。 適用於本發明之醇胺爲可與羥胺溶混的且較佳爲可溶 於水。此外，在本發明中有用之醇胺較佳具有相當高沸點 ，例如7 5 °C或更高。適合之醇胺爲一級，二級或三級胺 且較佳爲單胺|二胺或三胺·而最佳爲單胺。醇胺之醇基 較佳具有從1至6碳原子，且爲以線性，支鏈或環狀醇爲 基礎。 適合用於本發明之較佳醇胺可用下列化學式代表： RaRs-N-CHaCHa-O-Rs ’其中尺1與 R2 可爲 Η，CH3 ，CH3CH2 或 CH2CH20H 而 R3爲 CH2CH2〇H。 適合之醇胺之例子包括單乙醇胺’二乙醇胺，三乙 醇胺，第三丁基二乙醇胺，異丙醇胺，二異丙醇胺’ 2 - i紙ϋ適用中國國家標準（CNS ) A4規格（210X297公釐了 " -8 - (請先《讀背面之注意事項再填寫本f) «1 經濟部中央標準局員工消費合作社印製 r 4268 1 6 a7 ____B7_ 五、發明説明（6 ) 胺基一1一丙醇，3 —胺基—1 一丙醇，異丁醇胺，2_ 胺基一 2 -乙氧基乙醇（二甘醇胺），2 —胺基-2 —乙 氧基一丙醇與1 一羥基一 2 -胺基苯。 適合用於本發明之五倍子酸化合物具有下列結構式The abstract of the present invention is based on hydroxylamine compositions, as described in the previous applications and issued patents referred to above, which are commercially available from EKC Technologies, and the trustee of the present invention has proven to be very effective Removal formula for photoresist materials and etching residues in the integrated circuit industry. In the integrated circuit industry, due to continuous efforts to reduce critical dimensions • For example, component manufacturing below micron size, chemical compatibility and removal of etching residues used in wet processing procedures Used in very large-scale integrated circuits (VLS I) and excessively large-scale integrated circuits (ULS I 蟓 This paper is based on the common Chinese national standard (CNS) A4 washer (2 丨 0X297 mm) 4 268 1 6 A7 _B7_ V. Description of the Invention (3)) Obtaining an acceptable yield in the procedure becomes very, very critical. The composition of such an etching residue is generally composed of an etched substrate ', a substrate, a photoresist material, and an etching gas. The compatibility of wafers with wet chemicals, such as the suitability of hydroxylamine compositions, is highly opaque polysilicon, multilayer interconnect dielectric layers and gold spray coating in thin film coatings, wafer etching and post-etching processes However, it is usually quite different to switch from one manufacturing method to another. In some environments, hydroxylamine compositions, such as those containing catechol (1,2-dihydroxybenzene) • are corrosive on some gold substrates, such as on metal substrates that include titanium gold substrates or Substrates including aluminum layers are subject to corrosion at high temperatures, meaning more than 65 ° C. Chin has been widely used in semiconductor manufacturing processes. The two are used as a barrier layer to avoid the movement of electrons of certain atoms and as an anti-reflection layer on top of other metals. Catechol is considered a hazardous substance under the applicable US federal government regulations (S E RA Title E). In the semiconductor industry, in order to promote the introduction of more efficient and less toxic chemical products, research has been conducted to find products suitable for replacing catechol in hydroxylamine compositions. Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs (please read the note on the back before filling in this!) Therefore, the purpose of the present invention is to provide an improved hydroxylamine-based composition and use of this type The composition is a method suitable for meeting current semiconductor manufacturing requirements. Another object of the present invention is to provide a method suitable for removing photoresist materials and other polymer materials and residues from wafers and other substrates including ~ or multiple titanium metal layers. Compositions and methods that do not attack such titanium layers. A further object of the present invention is to provide a healthier product that does not apply the Chinese National Standard (CNS) A4 specification (210 × 297 mm) to this paper size. ___B7_V. Description of the invention (4) Compositions and methods of chemicals that cause pollution to the environment. These achievements and related purposes can be achieved by using the hydroxylamine-gallic acid compound compositions and methods invented here. The hydroxylamine monogallic acid compound composition of the present invention comprises a hydroxylamine compound, at least one alcoholamine compound and gallic acid compound that are miscible with the hydroxylamine compound. * According to the present invention, the photoresist material or other polymeric substance or residue is removed from the substrate. The method includes contacting the substrate with hydroxylamine compounds, alcoholamine compounds and gallic acid compounds that are miscible with hydroxylamine compounds at a temperature sufficient to remove the photoresist material, other polymer materials or residues. Actual In the above, it was found that catechol was replaced with an almost equal amount of gallic acid compound for removing the residue or peeling off The photoresist material is washed to at least about three times less than the eroded phenolic composition. However, compositions containing gallic acid compounds are obtained as a composition for removing residue or peeling and washing the photoresist material. Same performance. Achievements and related objectives, benefits and features of the present invention previously described will be apparent to those skilled in the art after reviewing the following more detailed description and graphics of the present invention. 1 to 4 are graphs showing the comparison results of the thickness measurement of titanium after the treatment with another composition for peeling, washing and removing the residue, and after the composition for peeling, washing and removing the residue according to the present invention, Figures 5 A — 1 4 B are scanning electron microscope (S EM) photographs showing the comparison results achieved by using the composition and method of the present invention. The paper dimensions are in accordance with the Chinese National Standard (CNS) A4 specification (2lOX25 > 7 mm) (please read the precautions on the back before filling out this page) Order 41 1 7-Consumption Cooperation by Employees of the Central Bureau of Standards, Ministry of Economic Affairs 4 2 6 8 16 A7 _____B7 V. Description of the invention (5) Detailed description of the present invention The hydroxylamine suitable for use in the present invention has the structural formula H2N — 0Η. The characteristics of hydroxylamine in many methods are hydrazine, Η2N-ΝΗ2, and hydrogen peroxide, Between HO and OH, it is displayed according to its suggested chemical formula. In pure form, hydroxylamine is a colorless dissolved solid with a melting point of 3 3 ° C. It is exposed to heat and slowly decomposes when heated. At ambient temperature or room temperature The extracted nitrogen and nitrous oxide * hydroxylamine are commercially available from Nissin Chemical Company as an aqueous solution of about 50% by weight in water. Ni Xin Chemical Company has added a suitable stabilizer to this solution to improve its storage. Stability. In fact, the commercially available form of this hydroxylamine is used in the present invention with reference to the detailed amount of the commercially available form. Hydroxylamine is incompatible with titanium as reported by the manufacturer. The alcohol amines suitable for use in the present invention are miscible with hydroxylamine and are preferably soluble in water. In addition, the alcohol amine useful in the present invention preferably has a relatively high boiling point, such as 75 ° C or higher. Suitable alcohol amines are primary, secondary or tertiary amines, and preferably monoamines | diamines or triamines, and most preferably monoamines. The alcohol group of the alcohol amine preferably has from 1 to 6 carbon atoms and is based on a linear, branched or cyclic alcohol. The preferred alcohol amines suitable for use in the present invention can be represented by the following chemical formula: RaRs-N-CHaCHa-O-Rs' wherein the ruler 1 and R2 may be Η, CH3, CH3CH2 or CH2CH20H and R3 is CH2CH2OH. Examples of suitable alcohol amines include monoethanolamine 'diethanolamine, triethanolamine, tertiary butyldiethanolamine, isopropanolamine, diisopropanolamine' 2-i paper ϋ applicable to China National Standard (CNS) A4 specifications (210X297 Millimeter " -8-(please read the notes on the back before filling in this f) «1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs r 4268 1 6 a7 ____B7_ 5. Description of the invention (6) Amine 1-propanol, 3-amino-1, 1-propanol, isobutanolamine, 2-amino- 2 -ethoxyethanol (diethylene glycol amine), 2-amino-2-ethoxymonopropanol With 1-hydroxy-2-aminobenzene. Gallic acid compounds suitable for use in the present invention have the following structural formula
0H0H
其中R爲氫，包含從1至1 〇碳原子之烷基或芳香基，而 X爲氫，鹵素或包括從1至5碳原子之烷基》較佳之五倍 子酸化合物爲五倍子酸，意即R與X爲氫，或五倍子酸丙 酯 > 意即R爲丙基而X爲氫。 所期望之組合物包括至少約5重量％羥胺，至少約 1 0重量％之至少一醇胺及從約2重量％至約3 0重量％ 之五倍子酸化合物"該組合物之平衡係由水，較佳爲高純 度去離子水，或其他適合之極性溶劑所構成。溶劑可單一 或以混合物使用《較佳之組合物包括從約5重量％至約8 0重量％羥胺，從約1 0重量％至約8 0重量％之至少一 醇胺，從約5重量％至約3 0重量％之五倍子酸化合物， 並以水或其他適合之極性溶劑保持平衡。 然而申請者不打算由任何特殊之理論束縛住’相信在 組合物中醇胺原地與五倍子酸化合物反應而形成醯胺或酚 胺鹽》 適合於該組合物之極性溶劑之例子除了水之外’亦包 本紙張尺度通用中國國家標準（CNS ) Α4規格（210Χ297公釐） {請先閲讀背面之注意事項再填寫本頁) 、1Τ 線 Γ 426816 Α7 ___;_Β7_ 五、發明説明（7 ) 括二甲亞硯，乙二醇，乙二醇烷基醚，二乙二醇烷基醚， 三乙二醇烷基醚，丙二醇，丙二醇烷基醚，二甲亞碉，N —輕取代之吡咯酮，伸乙基二胺與伸乙基三胺。在此技藝 所已知之額外極性溶劑亦可使用於本發明之組合物中。 本組合物之剝離與洗滌組合物在移除廣大範圍正光阻 材料是有效的，但特別有用於移除一般由正一棻醌二疊氣 化物磺酸酯或具有酚醛清漆型式黏合劑或樹脂之醯胺感光 劑所組成之光阻材料。商業上可購買到之光阻材料組合物 (本發明之剝離與洗滌組合物可有效地從受質上將其移除 )包括K. T. I.光阻材料820，825 :菲立浦（ Philip ) A.漢特（Hunt )化學股份公司Way coat HPR104，HPRl〇6 -HPR204 與 HPR 2 0 6光阻材料；序普雷（Shipley )公司之A Z — 1 300 系列，AZ-1400 系列與 AZ — 2400 系 列之光阻材料；與東京歐卡？C又（Tokyo Ohka Kogyo ) 股份有限公司之光阻材料OFPR—8 0 0 p 經濟部中央標隼局員工消t合作社印製 (請先閲讀背面之注意事項再填寫本頁) 另外，本發明之剝離與洗滌組合物甚至當聚醯亞胺塗 層遭受高溫固化，包括高至約4 0 0 °C之固化操作，亦可 從受質上移除聚醯亞胺塗層。商業上可購買到之聚醯亞胺 組合物之例子（本發明之剝離與洗滌組合物可有效地從受 質上將其移除）包括西巴給巨（Ciba Geigy )Wherein R is hydrogen, an alkyl or aromatic group containing from 1 to 10 carbon atoms, and X is hydrogen, and a halogen or an alkyl group containing 1 to 5 carbon atoms is preferred. The gallic acid compound is gallic acid, meaning R And X is hydrogen, or propyl gallic acid > means that R is propyl and X is hydrogen. Desirable compositions include at least about 5% by weight hydroxylamine, at least about 10% by weight of at least monoalcoholamine, and from about 2% to about 30% by weight gallic acid compounds " the balance of the composition is from water It is preferably composed of high-purity deionized water or other suitable polar solvents. Solvents can be used singly or as a mixture. Preferred compositions include from about 5% to about 80% by weight of hydroxylamine, from about 10% to about 80% by weight of at least one alcohol amine, and from about 5% to about 5% by weight. About 30% by weight of gallic acid compound, and keep balance with water or other suitable polar solvents. However, the applicant does not intend to be bound by any particular theory. 'It is believed that alcohol amines react with gallic acid compounds in situ in the composition to form amidine or phenamine salts.' Examples of polar solvents suitable for the composition other than water 'Also included in this paper is the General Chinese National Standard (CNS) A4 specification (210 × 297 mm) {Please read the precautions on the back before filling this page), 1T line Γ 426816 Α7 ___; _Β7_ 5. Description of the invention (7) Dimethyl sulfene, ethylene glycol, ethylene glycol alkyl ether, diethylene glycol alkyl ether, triethylene glycol alkyl ether, propylene glycol, propylene glycol alkyl ether, dimethyl sulfene, N-lightly substituted pyrrole Ketones, ethylenediamine and ethylenetriamine. Additional polar solvents known in the art can also be used in the compositions of the present invention. The stripping and washing composition of the present composition is effective in removing a wide range of positive photoresist materials, but it is particularly useful for removing sulfonate that is generally composed of n-quinone diazide gas sulfonate or a novolak type adhesive or resin. Photoresist material composed of fluorene sensitizer. Commercially available photoresist material compositions (the stripping and washing compositions of the present invention effectively remove them from substrates) include KTI photoresist materials 820, 825: Philip A. Han (Hunt) Chemical Co., Ltd. Way coat HPR104, HPR106-HPR204 and HPR 206 photoresist materials; Shipley's AZ-1300 series, AZ-1400 series and AZ-2400 series light Materials; and Tokyo Oka? C. (Tokyo Ohka Kogyo) Co., Ltd. Photoresist material OFPR-8 0 0 p Printed by a cooperative of employees of the Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back before filling out this page) In addition, the invention The peeling and washing composition can remove the polyimide coating from the substrate even when the polyimide coating is subjected to high temperature curing, including curing operations up to about 400 ° C. Examples of commercially available polyimide compositions (the stripping and washing compositions of the present invention effectively remove them from the substrate) include Ciba Geigy
P r o i m i d e 2 9 3 ，阿薩喜（A s a h ί ) G—6246 — S ，與杜邦（DuPont )PI 2545 與 PI 2555。 以本發明之剝離與洗滌組合物移除受質上之光阻材料 本紙張尺度適用中國國家揉隼（CNS ) A4規格（2〖0X297公釐） -10 - Α7· ^ 426816 B7 五、發明説明（8 ) (請先閱讀背面之注意事項再填寫本頁) 且不會侵蝕受質本身之受質例子，包括金屬受質，例如鋁 ，鈦，鎢，鈦/鎢/鋁/矽/銅；及例如氧化矽•氮化矽 ，與鎵/砷化物之受質；及例如聚碳酸酯之塑膠受質。 本發明之剝離與洗滌組合物對移除所利用之蝕刻設備 之受質上所產生之有機金屬與金屬氧化物剩餘物亦是有效 的。商業上可購買到之蝕刻設備之例子包括可從雷姆研究 (Lam Research ) ， Tegal, Electrotech, Applied M a t e r i a 1 s ·東京電子（T o k y ο E 1 e c 1: r ο n )，日立與類 似之單位購得β 從受質上使用本發明之剝離與洗滌組合物移除阻礙物 或其他物質之方法包括在足夠移除該阻礙物之溫度，將在 其上具有阻礙物之受質與本發明之剝離與洗滌組合物接觸 一段時間。時間與溫度係以從受質上所移除之特殊材料爲 基礎而決定。通常，溫度爲從約週遭溫度或室溫至約 120 °C之範圍，而接觸時間爲從約2至60分鐘β 經濟部中央標準局貝工消費合作社印製 使用本發明之剝離與洗滌組合物剝離與洗滌受質之方 法包括在足夠移除剩餘物之溫度，將在其上具有有機金屬 與金屬氧化物剩餘物之受質與本發明之剝離與洗滌組合物 接觸一段時間。時間與溫度係以從受質上所移除之特殊材 料爲基礎而決定，通常，溫度係在從約週遭或室溫至約 1 20 °C之範圍，而接觸時間爲從約2至60分鐘。 在任何一個例子中，受質以極性溶劑潤洗，例如異丙 醇，接著以去離子水潤洗。然後該受質經機械乾燥，例如 以旋轉乾燥機，或吹氮氣乾燥。 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公釐） 11 A7 4268 1 6 _____B7 ____ _ 五、發明説明（9 ) 下列例子用以更進一步描述本發明但非代表限制本發 明之範圍* 根據本發明適合用於從受質移除阻礙物或從受質上移 除阻礙物或其他有機剩餘物之剝離與洗滌組合物之例子於 下表1中提出。組合物A與G爲用於做爲與包含五倍子酸 化合物組合物所獲得之結果參考比較之比較組合物。組合 物爲在下列例子中用於移除光阻材料與剩餘物之先前技藝 組合物。P r o i mi d e 2 9 3, Asahi G-6246-S, and DuPont PI 2545 and PI 2555. The photoresist material on the substrate is removed by the peeling and washing composition of the present invention. The paper size is applicable to the Chinese national standard (CNS) A4 (2 〖0X297mm） -10-Α7 · ^ 426816 B7 V. Description of the invention (8) (Please read the notes on the back before filling this page) Examples of substrates that do not erode the substrate itself, including metal substrates, such as aluminum, titanium, tungsten, titanium / tungsten / aluminum / silicon / copper; And substrates such as silicon oxide, silicon nitride, and gallium / arsenide; and plastic substrates such as polycarbonate. The peeling and washing composition of the present invention is also effective for removing organometallic and metal oxide residues produced on the substrate of the etching equipment used. Examples of commercially available etching equipment include those available from Lam Research, Tegal, Electrotech, Applied Materials 1 s · Tokyo Electronics (Toky ο E 1 ec 1: r ο n), Hitachi and similar The method for removing β from a substrate using the stripping and washing composition of the present invention to remove an obstacle or other substance includes a temperature and temperature sufficient to remove the obstacle, which will have the substrate and the substrate thereon. The peel of the invention is in contact with the cleaning composition for a period of time. Time and temperature are determined based on the special materials removed from the substrate. Generally, the temperature ranges from about ambient temperature or room temperature to about 120 ° C, and the contact time is from about 2 to 60 minutes. Β Printed using the peeling and washing composition of the present invention by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The method of peeling and washing the substrate includes contacting the substrate having the organometallic and metal oxide residue thereon with the peeling and cleaning composition of the present invention for a period of time at a temperature sufficient to remove the residue. Time and temperature are determined based on the special material removed from the substrate. Generally, the temperature is in the range from about ambient or room temperature to about 120 ° C, and the contact time is from about 2 to 60 minutes . In either case, the substrate is rinsed with a polar solvent, such as isopropyl alcohol, followed by deionized water. The substrate is then dried mechanically, for example by a rotary dryer, or by blowing nitrogen. This paper size applies to China National Standards (CNS) A4 specifications (210X297 mm) 11 A7 4268 1 6 _____B7 ____ _ V. Description of the invention (9) The following examples are used to further describe the invention but not to limit the scope of the invention * Examples of stripping and washing compositions suitable for removing obstructions from substrates or removing obstructions or other organic residues from substrates according to the present invention are presented in Table 1 below. Compositions A and G are comparative compositions used as a reference comparison with results obtained with gallic acid compound-containing compositions. The composition is a prior art composition for removing photoresist materials and residues in the following examples.
表I 剝離 商業上 額外 (請先閲讀背面之注意事項再填寫本瓦) 經濟部中央標準局貞工消费合作社印装 與 洗 滌 之羥胺 Λ 醇胺 添加物 之溶劑 辆 物 w t. 9ίί w t. % w t . .% A 35¾ 60¾單 乙 醇 胺 5¾兒 苯 酚 B 35¾ 60¾單 乙 醇 胺 5%五 倍 子 酸 C 30¾ 60¾單 乙 醇 胺 10¾五 倍 子 酸 D 30¾ 60¾異 丙 醇 胺 10¾五 倍 子 酸 E 45% 45% 二 甘 醇 胺 10%五 倍 子 酸 F 0 50¾ 二 甘 醇 胺 50%N -乙基 羥 基-2 -吡咯 酮 G 35¾ 60¾ 二 甘 醇 胺 5%兒 苯 酚 Η 30% 60¾ 二 甘 醇 胺 1 0¾五 倍 子 酸 丙脂 I 30% 55¾ 二 甘 酵 胺 1 0¾五 倍 子 酸 5¾水 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12 - 經濟部中央揉準局員工消费合作社印製 4 2β8 1 6 Α7 _____Β7_ 五、發明説明（1〇 ) J 30¾ 55%二甘醇胺10¾五倍子酸5¾二甲亞碉 K 30¾ 30¾二甘醇胺10¾五倍子酸 30¾單乙醇胺 L 35¾ 60%異丙醇胺 5%五倍子酸 M 20¾ 55¾單乙醇胺15¾五倍子酸10¾水 *包括近乎5 0重量％水 例1 此例顯示在羥胺剝離與洗滌組合物中，五倍子酸取代 兒苯酚，使得該剝離與洗滌組合物在半導體晶片上對鈦冶 金之腐蝕性小於包含兒苯酚之剝離與洗滌組合物。在半導 體製造中所使用冶金薄膜之尺寸改變可藉由使用下列方程 式，藉由量測其薄膜電阻而決定： 薄膜電阻二電阻率/薄膜厚度 以具有3 5 0 0 _ 4 0 0 0埃極微小厚度之經陰極濺 鍍之鈦薄膜晶片進行實驗（如藉由使用普若米吉克斯（ Prometrix )四點探針量測薄膜電阻而決定厚度）。在 7 5 °C *將晶片樣本浸漬於列示於表1中之組合物A，B ，C，D，G與I中各30，60與1 20分鐘》較高之 量測薄膜電阻起因於鈦薄膜之較大腐蝕。 圖1 一 4爲以殘留厚度百分比對時間所繪曲線之形式 之所得測量圖形。圖1爲組合物A與B之比較（在乙酸胺 系統中*兒苯酚對五倍子酸）。圖2爲組合物G與I之比 較（在二甘醇胺系統中，兒苯酚對五倍子酸）*圖3爲組 本纸張尺度適用中國國家標準（CNS ) Μ規格< 210X297公釐） (請先W讀背面之注意Ϋ項再填寫本頁) -* 咴 -13 - * 426816 A7 B7 經濟部中央標準局員工消費合作社印装 五、發明説明（U ) 合物B與C之比較，顯示在乙醇胺系統中五倍子酸濃度之 影響。圖4爲組合物C與D之比較（在乙醇胺系統中之五 倍子酸對在異丙醇胺系統中之五倍子酸）。 圖1清楚地顯示在除了組合物B與組合物A以外，在 相同之羥胺剝離與洗滌溶液中，包含五倍子酸之剝離與洗 滌組合物B較先前技藝包含兒苯酚之剝離與洗滌組合物A 有較小之鈦腐蝕β 例2 使用組合物Μ顯示本發明同樣從晶片表面上移除流動 離子污染物。依下列方法製備用以評價流動離子污染物之 晶片樣本，由T i N/A5S i/T i N/T i所組成之 金屬薄膜濺鍍鍍層在四乙基矽酸硼（B TEO S )晶片上 。然後該晶片以光阻材料加上圖案並在電漿蝕刻系統中蝕 刻該金屬薄膜•藉由氧電漿灰化移除光阻材料。在7 5 °C 在組合物Μ加工前與後3 0分鐘，藉由S I MS探針測量 在BTEOS上之污染物》在噴霧沖洗器中，所有樣本以 去離子水沖洗五循環。然後以氮槍乾燥樣本。表2顯示有 與沒有以組合物Μ加工所獲得之結果。 表2 在溶液中Na 在BTE0S表面上 含量（DDm ) Na含量原子/公分2 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐）~ (請先Μ讀背面之注意事項再填寫本页) 訂 —14 - 4268 1 6 A7 B7 經濟部中央搮準局貞工消费合作社印製 五、 發明説明 ( 12 ) - 未 經 加 工 之 晶 片 一 L ] 6 X 0 1 1 組 合 物 Μ 90. 9 1 .1 8 X 1 03 1 ，| 請 此 結 果 顯 示 組 合 物 Μ 可 從 晶 片 表 面 上 移 除 鈉 0 先 閲 讀 背 .1 A 之 例 3 注 意 事 在 氧 化 矽 介 電 層 中 具 有 1 2 微 米 大 小 之 通 路 開 □ 1 項 再 填 使 用 標 準 氧 化 矽 電 漿 蝕 刻 方 法 對 遍 及 光 阻 材 料 圖 案 化 之 開 寫 本 頁 □ 進 行 餓 刻 » 藉 由 氧 電 漿 灰 化 而 移 除 光 阻 材料 g 圖 5 A 爲 掃 描 電 子 顯 微 鏡 ( S E Μ ) 1 w.i 圖 像 之 顯 微 照 相 » 顯 示 置 有機 金 屬 蝕 刻 剩 餘 物 殘 留 在 受 質 表 面 上 特 別 是 在 通 路 開 孔 附 近 〇 然 後 在 7 0 ac 該 受 質 在 組 合 物 B 中 加 工 3 0 分 鐘 Λ 訂 圖 5 B 所 得 之 S E Μ 照 片 顯 fWSK 示 組 合 物 B 移 除 所 有 有 機 金 靥 殘 餘 物 〇 唆 例 4 在 氧 化 矽 介 電 層 中 上 面 覆 蓋 有 T i N / A 9. — s' i — C U 金 屬 薄 膜 在 薄 膜 上 具 有 0 6 微 米 大 小 之 通 路 開 孔 » 使 用 標 準 之 氧 化 矽 電 漿 蝕 刻 方 法 i 經 光 阻 材 料 繪 製 圖 案 開 孔 而 進 行 蝕 刻 0 使 用 氧 電 漿 灰 化 移 除 光 阻 材 料 9 圖 6 A 與 6 B t S E Μ 顯 微 照 相 » 顯 示 重 蝕 刻 剩 餘 物 殘 留 在 通 路 .1 開 孔 上 〇 圖 6 C 之 顯 微 照 相 顯 示 在 7 0 °C 在 以 組合 物 E 加 1 工 3 0 分 鐘 之 後 > 組 合 物 Ε 完 全 地 移 除 所 有 剩 餘 物 〇 組 合 物 F » 種 包 含 Ν — 乙 基 羥 基 — 2 — 吡 咯 酮 之 商 業 上 可 購 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 426816 A7 B7 五、發明説明（13 ) 買到之光阻材料剝離劑1在1 2 0°C加工3 0分鐘之後， 部份地移除触刻剩餘物，如圖6 D所示。 例5 此例顯示以掊酸丙酯取代兒苯酚之剝離與洗滌組合物 之可操作性。在經電漿氧化物蝕刻通路之晶片上使用組合 物Η。氧電漿灰化通常接著電漿氧化物蝕刻加工步驟之後 進行。在此實驗中，爲了論證該剝離與洗滌組合物亦可移 除電漿蝕刻處理過之光阻材料，在一些晶片上使用做爲通 路蝕刻遮罩之光阻材料未藉由氧電漿灰化步驟移除。圖 7 Α顯示在通路蝕刻之後，具有光阻材料層之通路晶片。 圖7 Β顯示在氧電漿灰化之後，在晶片表面上殘留有機金 屬與氧化物剩餘物。圖7 C與7D顯示在6 5 °C加工3 0 分鐘之後|在曝露至電漿氧化物蝕刻環境之後，組合物Η 有效地移除光阻材料，且在氧電漿灰化之後無困難地移除 殘留之有機金屬與氧化物剩餘物。 例6 此例顯示包含兒苯酚之組合物G與包含五倍子酸之組 合物I之不同腐蝕性。TiN/Al S i/Ti/TiN /T i冶金之三明治狀物金靥薄膜受質經繪製圖案並在電 漿金靥蝕刻劑中進行蝕刻。圖8 A顯示在藉由氧電漿灰化 移除光阻材料之後*有機金屬剩蝕物留在金靥線表面上。 在7 5 °C晶片曝露於組合物G 3 0分鐘之後，鈦阻擋層（ 本纸張尺度適用中國國家標準（CNS ) A4規格（2I0X297公釐> (請先聞讀背面之注意事項再填寫本页) -ί17 經濟部中央標準局貝工消費合作社印製 -16 - 426816 A7 經濟部中央樣準局貝工消費合作社印製 B7五、發明説明（14 ) T i/T i N/T i )遭凹蝕。在相同加工條件之下，包 含五倍子酸之剝離劑組合物I未侵蝕該阻擋層，如在圖8 C中所示。 例7 本例另外說明藉由包含五倍子酸之剝離與洗滌組合物 在鈦阻擋金屬薄膜上侵蝕之減少》在具有W/T i冶金之 電漿蝕刻晶片上進行試驗。藉由氧電漿灰化移除光阻材料 «在7 5 °C將晶片浸漬於剝離與洗滌溶液中3 0分鐘。鈦 阻擋層側面遭組合物（包含兒苯酚）嚴重侵蝕，如在圖 9 A中所示。包含五倍子酸之剝離與洗滌組合物I未具有 任何對鈦薄膜之影響，如在圖9 B中所示。 例8 此例顯示可添加額外之極性溶劑至羥胺/五倍子酸剝 離與洗滌之組合物中，不會影響其性能》圖1 0A與 1 Ο B顯示曾在7 5 °C在組合物J中加工3 0分鐘之電漿 蝕刻之金屬與通路晶片之結果。組合物J移除所有蝕刻剩 餘物而不會侵蝕鈦阻擋金靥層。 例9 此例論證組合物K，一種使用異丙醇胺做爲醇胺之羥 胺/五倍子酸剝離與洗滌組合物，移除所有蝕刻剩餘物而 不會侵蝕鈦阻擋金屬層°圖1 1A，1 1 B與1 1C顯示 (請先閱讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標丰{ CNS ) A4規格（210X297公釐） -17 - 經濟部中央標準局貝工消費合作社印製 4 2 68 16 47 A7 __B7五、發明説明（15 ) 在7 5 °C在組合物K中加工3 0分鐘之電漿蝕刻金屬與通 路晶片之結果》 例1 0 此例顯示包含五倍子酸之羥胺剝離與洗滌組合物可從 聚矽受質上移除後蝕刻光阻材料剩餘物。具有厚度約 4 0 0 nm之經蝕刻聚矽層之矽晶片浸漬於9 5 °C之組合 物I中，浸漬30，45與60分鐘》然後以氮槍乾燥晶 片。然後藉由日立S — 4 5 0 0 FE掃描電子顯微鏡（ 5 ΕΜ)檢査評價組合物移除蝕刻剩餘物之能力。 未經加工與加工晶片之S ΕΜ照片顯示於圖1 2Α， 1 2Β，1 2C，12D與12Ε中》大部份剩餘物在聚 矽線之側壁上，如在圖12Α與12Β中所示。在浸漬於 組合物I中3 0與4 5分鐘之後，移除大部份剩餘物，如 在圖1 2C與1 2D中所示。在浸漬於組合物I中60分 鐘之後*剩餘物完全地移除，如在圖1 2 Ε中所示，此爲 晶片製造可接受之加工條件。 例1 1 此例顯示五倍子酸同樣地與醇胺混合物妥善地進行。 組合物Κ爲包含乙醇胺與二甘醇胺之溶液》圖1 3 Α與 1 3 B顯示在7 5 °C以組合物K處理3 ◦分鐘與6 0分鐘 之後，在金屬與逋路蝕刻晶片中移除剩餘物但不會侵蝕鈦 阻擋金靥層之效果· 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注11^項再填寫本頁) 訂 -18 - d268 1 6 經濟部中央標準局貞工消费合作社印製 A7 B7 五、發明説明（16 ) 例1 2 組合物L ’其中醇胺爲異丙醇胺，當使用在7 5 °C加 工6 0分鐘，金屬與通路蝕刻不會侵蝕T i阻擋金靥層， 有效地移除所有蝕刻剩餘物，如在圖1 4 A中所示。圖 1 4 B論證從通路開口在洗滌之通路蝕刻剩餘物之效果。 摘要而言，上述例子顯示組合物B- E與H -L具有 在不同之晶片，例如金屬，通路與聚矽晶片上移除光阻材 料與蝕刻剩餘物之能力而不會對受質有不利之影響。這些 組合物在受質適合性上展現優異之性能，特別是在髙溫具 有丁 i與Aj?金爵薄膜（與組合物A，F與G比較）。組 合物B - E與H-L無包含經Section 313 of the Emergency Planning and Community Right-To-Know Act of 1986 and of 40 CFR372 記錄要求之 物質，不像組合物A與G。 現在對於熟知此技藝之人士關於本發明曾提供之新穎 組合物與所述目的之可達成方法是顯而易見的。以羥胺爲 基礎之經改良組合物與使用本發明之此類組合物之方法是 適合現今半導體製造要求。該組合物與方法是適合於從晶 片上移除光阻材料與其他聚合物質與剩餘物，亦適合於從 其他包含一或多鈦金屬層之受質上移除光阻材料與其他聚 合物質與剩餘物而在其後不會侵蝕此類鈦層》該組合物與 方法不包含或使用任何需經記錄要求之材料。 另外，如本發明所示與描述之不同形式變化與細節對 於熟知此技藝之人士是顯而易見可進行的。需注意的是如 本紙張尺度適用中國國家揉準{ CNS ) A4規格（210X297公釐） <請先Μ讀背面之注意事項再填寫本頁) ,11 -19 - r 4268 16 A7B7五、發明説明（17 ) 此之改變必需包含在此所附加之申請專利範圔之精神與範 圍之內β (請先聞讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局負工消費合作杜印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -20 -Table I Stripping of commercial extras (please read the notes on the back before filling in this tile) Solvents for hydroxylamine Λ alcoholamine additives printed and washed by the Central Standards Bureau of the Ministry of Economic Affairs, Zhengong Consumer Cooperative, w t. 9ί w t. % wt..% A 35¾ 60¾ monoethanolamine 5¾ phenol B 35¾ 60¾ monoethanolamine 5% gallic acid C 30¾ 60¾ monoethanolamine 10 ¾ gallic acid D 30¾ 60¾ isopropanolamine 10¾ gallic acid E 45% 45% diethylene glycol amine 10 % Gallic acid F 0 50¾ Diethylene glycol amine 50% N-ethylhydroxy-2 -pyrrolidone G 35¾ 60¾ Diethylene glycol 5% catechol 30% 60¾ Diethylene glycol amine 1 0¾ Gallic acid propyl I 30% 55¾ Diglycinamine 1 0¾ Gallic acid 5¾ Water The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -12-Printed by the Consumer Cooperatives of the Central Bureau of the Ministry of Economic Affairs 4 2β8 1 6 Α7 _____ Β7_ V. Description of the invention (1〇) J 30¾ 55% diethylene glycol amine 10¾ gallic acid 5¾ dimethylarsine K 30¾ 30¾ diethylene glycol amine 10¾ gallic acid 30¾ monoethanolamine L 35¾ 60% isopropanolamine 5% gallic acid M 20¾ 55¾ monoethanolamine 15¾ gallic acid 10¾ water * including almost 50% by weight water Example 1 This example shows the hydroxylamine stripping In gallic acid and cleaning compositions, gallic acid replaces catechol, so that the stripping and cleaning composition is less corrosive to titanium metallurgy on semiconductor wafers than the stripping and cleaning composition containing phenol. The size change of the metallurgical film used in semiconductor manufacturing can be determined by measuring its sheet resistance by using the following equation: Sheet resistance two resistivity / thin film thickness to have 3 5 0 0 _ 4 0 0 0 Angstroms The thickness of the cathode thin-film titanium thin film wafer is tested (eg, the thickness is determined by measuring the film resistance using a Prometrix four-point probe). At 7 5 ° C * The wafer samples were immersed in the compositions A, B, C, D, G, and I for 30, 60, and 1 20 minutes each as shown in Table 1. The higher measured film resistance is due to Large corrosion of titanium film. Figures 1 to 4 show the measurement patterns in the form of a percentage of residual thickness versus time. Figure 1 shows a comparison of compositions A and B (* catechol to gallic acid in an amine acetate system). Figure 2 shows the comparison of composition G and I (in the diethylene glycol amine system, catechol to gallic acid) * Figure 3 shows the paper size applicable to the Chinese National Standard (CNS) M specification < 210X297 mm) ( Please read the note on the back before filling this page)-* 咴 -13-* 426816 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (U) Comparison of compounds B and C, showing Effect of Gallic Acid Concentration in Ethanolamine System. Figure 4 shows a comparison of Compositions C and D (gallic acid in ethanolamine system versus gallic acid in isopropanolamine system). Figure 1 clearly shows that in the same hydroxylamine stripping and washing solution except for Composition B and Composition A, the peeling and washing composition B containing gallic acid is more effective than the stripping and washing composition A containing catechol in the prior art. Minor Titanium Corrosion β Example 2 The use of composition M shows that the present invention also removes mobile ionic contaminants from the wafer surface. A wafer sample for evaluating mobile ionic contamination was prepared according to the following method. A metal thin film consisting of T i N / A5S i / T i N / T i was sputter-coated on a tetraethyl boron silicate (B TEO S) wafer. on. The wafer is then patterned with a photoresist material and the metal film is etched in a plasma etching system. • The photoresist material is removed by oxygen plasma ashing. Contaminants on BTEOS were measured by SI MS probe at 75 ° C before and after processing of Composition M for 30 minutes. All samples were rinsed with deionized water for five cycles. The sample was then dried with a nitrogen gun. Table 2 shows the results obtained with and without processing with Composition M. Table 2 Na content in solution on the surface of BTE0S (DDm) Na content atom / cm 2 This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) ~ (Please read the precautions on the back before filling in this Page) Order—14-4268 1 6 A7 B7 Printed by Zhenong Consumer Cooperative of Central Bureau of Quasi-Ministry of Economic Affairs V. Invention Description (12)-Unprocessed Wafer 1 L] 6 X 0 1 1 Composition M 90. 9 1 .1 8 X 1 03 1 ， | This result shows that the composition M can remove sodium from the surface of the wafer. 0 Read the back. 1 A Example 3 Note that the silicon oxide dielectric layer has a size of 12 μm. Path Opening □ 1 refilling open book using standard silicon plasma etching method to pattern photoresist material Page □ Carved out »Removal of photoresist material by oxygen plasma ashing Figure 5 A is a photomicrograph of a scanning electron microscope (SEM) 1 wi image» It is shown that the residue of the organic metal etching remains on the substrate The surface of the substrate is especially near the opening of the channel. Then, the substrate is processed in composition B for 30 minutes at 70 ac. The SE Μ photo obtained from Fig. 5B shows fWSK showing that composition B removes all organic gold. Residues Example 4 The silicon oxide dielectric layer is covered with T i N / A 9. — s' i — CU metal film with 0 6 micron via openings in the film »using standard silicon oxide Paste etching method i Use a photoresist material to draw a pattern to make holes. 0 Oxygen plasma ashing is used to remove the photoresist material. 9 Figure 6 A and 6 B t SE Μ Photomicrographs »shows that the re-etching residues remain on the vias. 1 Openings. The photomicrograph of Fig. 6C shows that at 70 ° C after 30 minutes with composition E plus composition E completely Remove all residues. Composition F »Commercially available paper containing N-ethyl hydroxyl-2-pyrrolidone. This paper is compliant with China National Standard (CNS) A4 (210X 297 mm) 426816 A7 B7 V. Description of the invention (13) The commercially available photoresist stripper 1 is partially removed after processing at 120 ° C for 30 minutes, as shown in Fig. 6D. Example 5 This example shows the operability of a peeling and washing composition in which catechol is substituted with propyl gallate. Composition VII is used on wafers that have been etched via plasma oxide. Oxygen plasma ashing is usually followed by a plasma oxide etching process step. In this experiment, in order to demonstrate that the stripping and cleaning composition can also remove the photoresist material treated by plasma etching, the photoresist material used as a via etching mask on some wafers was not ashed by oxygen plasma. Step removed. FIG. 7A shows a via wafer with a photoresist material layer after via etching. Fig. 7B shows that organic metal and oxide residues remain on the wafer surface after the oxygen plasma ashing. Figures 7C and 7D show that after processing for 30 minutes at 65 ° C | after exposure to the plasma oxide etching environment, the composition Η effectively removed the photoresist material, and without difficulty after the oxygen plasma ashing Remove residual organometallic and oxide residues. Example 6 This example shows the different corrosivity of composition G containing catechol and composition I containing gallic acid. TiN / Al S i / Ti / TiN / T i metallurgy sandwich-shaped Au film was subjected to a pattern drawing and etched in a plasma Au film etchant. FIG. 8A shows that after the photoresist material is removed by oxygen plasma ashing, an organometallic residue remains on the surface of the gold wire. After 30 minutes of exposure at 75 ° C to the composition G, the titanium barrier layer (this paper size applies the Chinese National Standard (CNS) A4 specification (2I0X297 mm >) (Please read the precautions on the back before filling (This page)-ί17 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-16-426816 A7 Printed by the Shellfish Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs B7 V. Description of the invention (14) T i / T i N / T i ) Was etched. Under the same processing conditions, the release agent composition I containing gallic acid did not attack the barrier layer, as shown in FIG. 8C. Example 7 This example also illustrates that Reduction of Erosion of Detergent Compositions on Titanium Barrier Metal Films "Test on Plasma Etched Wafers with W / T i Metallurgy. Removal of Photoresist Material by Oxygen Plasma Ashing« Dip the wafer at 7 5 ° C 30 minutes in peeling and washing solution. The side of the titanium barrier layer was severely eroded by the composition (containing phenol), as shown in Figure 9A. The peeling and washing composition I containing gallic acid did not have any anti-titanium film. The effect is as shown in Figure 9B. Example 8 This example It shows that an additional polar solvent can be added to the hydroxylamine / gallic acid peeling and washing composition without affecting its performance. "Figures 10A and 10B show that it has been processed in composition J for 30 minutes at 7 5 ° C. Results of plasma etching of metal and via wafers. Composition J removes all etching residues without eroding the titanium barrier gold layer. Example 9 This example demonstrates Composition K, an isopropanolamine as an alcoholamine Hydroxylamine / gallic acid peeling and washing composition, removes all etching residues without eroding the titanium barrier metal layer. Figure 1 1A, 1 1 B and 1 1C (Please read the precautions on the back before filling this page) Order This paper size applies to China National Standard Feng (CNS) A4 specification (210X297 mm) -17-Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 2 68 16 47 A7 __B7 V. Description of the invention (15) at 7 5 ° C. Results of plasma etching metal and via wafer processed in composition K for 30 minutes. Example 1 0 This example shows that the hydroxylamine stripping and cleaning composition containing gallic acid can be removed from the polysilicon substrate and the photoresist is etched. Material residue. A silicon wafer having an etched polysilicon layer having a thickness of about 400 nm was immersed in Composition I at 95 ° C, immersed for 30, 45, and 60 minutes, and then the wafer was dried with a nitrogen gun. The ability of the composition to remove the etching residue was then examined by a Hitachi S-4500 FE scanning electron microscope (5 EM) inspection. The S EM photographs of the unprocessed and processed wafers are shown in Figures 12A, 12B, 12C, 12D, and 12E. Most of the residues are on the side walls of the polysilicon wire, as shown in Figures 12A and 12B. After immersing in Composition I for 30 and 45 minutes, most of the residue was removed, as shown in Figures 12C and 12D. After 60 minutes of immersion in composition I * the residue was completely removed, as shown in Figure 12E, which is an acceptable processing condition for wafer fabrication. Example 11 This example shows that gallic acid works well with alcohol amine mixtures. Composition K is a solution containing ethanolamine and diethylene glycol amine. "Figures 13 A and 1 B show treatment with composition K at 75 ° C for 3 ◦ and 60 minutes in a metal and Kushiro etched wafer The effect of removing the residue without eroding the titanium barrier layer of gold · This paper size applies to the Chinese National Standard (CNS) A4 size (210X 297 mm) (Please read Note 11 ^ on the back before filling this page) Order -18-d268 1 6 A7 B7 printed by Zhengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (16) Example 1 2 Composition L 'wherein the alcohol amine is isopropanolamine, when used at 7 5 ° C for processing At 60 minutes, the metal and via etch will not erode the Ti blocking layer, effectively removing all etch residues, as shown in Figure 14A. Figure 14B demonstrates the effect of etching the residue from the via opening in the washed via. In summary, the above examples show that the compositions B-E and H-L have the ability to remove photoresist materials and etch residues on different wafers, such as metals, vias, and polysilicon wafers without adversely affecting the quality. Influence. These compositions exhibit excellent properties in terms of substrate suitability, and in particular, have i and Aj? Jinjue films (compared to compositions A, F, and G) at high temperatures. Compositions B-E and H-L do not contain substances required by Section 313 of the Emergency Planning and Community Right-To-Know Act of 1986 and of 40 CFR372 records, unlike Compositions A and G. It will now be apparent to those skilled in the art regarding the novel composition and the achievable method of the stated purpose provided by the present invention. Improved hydroxylamine-based compositions and methods of using such compositions of the present invention are suitable for today's semiconductor manufacturing requirements. The composition and method are suitable for removing photoresist materials and other polymer materials and residues from wafers, and are also suitable for removing photoresist materials and other polymer materials and materials from other substrates containing one or more titanium metal layers. The remainder does not erode such titanium layers thereafter. The composition and method does not include or use any materials that require documentation. In addition, variations and details of the different forms shown and described in the present invention will be apparent to those skilled in the art. It should be noted that if this paper size applies to the Chinese national standard {CNS) A4 specification (210X297 mm) < Please read the notes on the back before filling this page), 11 -19-r 4268 16 A7B7 V. Invention Note (17) This change must be included in the spirit and scope of the patent application scope attached here β (please read the notes on the back before filling this page). The paper size for printing is applicable to China National Standard (CNS) A4 specification (210X 297 mm) -20-