200536936 九、發明說明： 【發明所屬之技術領域】 本發明係關於用⑨洗淨微電子物基板之方法及洗淨餘刻 後及/或光阻劑灰分殘餘物之含水組合物。當該等微電子物 基板經受洗淨及隨後水漂洗時本發明之組合物提供對金屬 之增強保護，即，抑制腐蝕。 【先前技術】 已將許多光阻劑剝離劑及殘餘物移除劑提議作為製造線 路洗淨劑之下游或末端而用於微電子物領域。在製程中將 一光阻劑薄膜沈積於-基板物質上，且隨後電路設計顯影 於。亥薄膜上。烘培後將經曝光之抗蝕劑用光阻劑顯影劑移 除卩通後藉由電名餘刻劑氣體或化學餘刻劑溶液將所得影 像轉移至-般為介電質或金屬之下層物質上。蝕刻劑氣體 或化子餘刻劑溶液選擇性地侵餘基板之未受光阻劑保護區 域電水钱刻裝程的結果為光阻劑及經钱刻物質之副產物 以殘餘物形式沈積於基板及光阻劑上之經餘刻開口周圍或 側壁上。 另外，蝕刻步驟終止後須將抗蝕劑遮罩自基板之受保護 區域移除以便進行下一製程操作。此可藉由使用適當之電 漿灰化氣體或濕式化學剝離劑經電漿灰化步驟達成。發現 適虽之用於移除該抗蝕劑遮罩物之洗淨組合物且無不利 〜響例如，腐蝕、蝕刻或鈍化，金屬電路亦證明有問題。 由於微電子物製造集成度提高及圖案化微電子物裝置尺 寸的下降’因此提供適當之具有適當剝離及洗淨特性且不 96961.doc 200536936 產生其他不利影響之光阻劑剝離及洗淨 ^ A σ物則愈加困 難。在半導體及平板顯示器（FPD)領域，尤其當選擇如銘 鈦及鎢及合金之金屬來使用時，光阻劑剝離、殘餘物移除 及水〉示洗過程中之金屬腐姓問題為一嚴重缺陷。 ’' 用於微電子物應用之典型殘餘物移除劑可為含鹼組合 物，其包括與有機胺或羥胺及其他溶劑化劑摻合之極性= 機溶劑以試圖減輕金屬及介電質侵蝕或腐蝕。胺及羥胺已 顯示出於溶劑摻合物中具有增強光阻劑及殘餘物移除之功 效。然而，該等鹼性灰分殘餘物移除調配物經歷自空氣中 之二氧化碳吸收，大多數情況下縮短洗淨劑溶液之有效鍍 浴時間。此外，該等鹼性洗淨劑組合物起作用相對緩慢且 需要將該等基板於高溫下置於於該等洗淨溶液中歷經延長 之時間。此外，使用該類移除劑後之水漂洗可生成一強鹼 性水溶液，其可導致相當多的金屬自圖案化線路損失。^ 就使得洗淨/剝離步驟與水漂洗之間的中間漂洗成為必 要。該中間漂洗通常使用異丙醇，對於製程增加不必要的 時間、安全考慮、環境影響及成本。 因此需要用於光阻劑及殘餘物之剝離及洗淨組合物，其 能將蝕刻劑及/或灰分殘餘物自微電子物基板完全移除，特 定言之需要該等不產生任何顯著金屬腐蝕之洗淨劑及殘餘 物移除組合物。 【發明内容】 本發明提供用於洗淨微電子物基板之含水洗淨組合物， 其基本上能完全洗淨該等基板且對於該等基板之金屬元件 96961.doc 200536936 基本上不產生金屬腐钱，且與先前技術之含鹼洗淨組合物 所需之洗淨時間相比其洗淨時間相對短且於相對低溫下進 订。本發明亦提供一種使用該等含水洗淨組合物洗淨微電 子物基板之方法，特定言之為FPD微電子物基板，且對於 该微電子物基板之金屬元件不產生任何顯著金屬腐餘。本 發明之含水洗淨組合物包含（a)水、（b)銨或第四銨離子中之 至少一種及（c)次磷酸根（H2P〇2·)或亞磷酸根（Hp〇32·)離子 中之至少一種。應瞭解銨與第四銨離子可同時存在於本發 明之組合物中，且次磷酸根與亞磷酸根離子亦可同時存在 於本發明之組合物中。本發明之另一實施例中，本發明之 洗淨組合物較佳亦含有氟離子。本發明之洗淨組合物視情 況可於組合物中存在其他組份，如例如界面活性劑、金屬 錯合劑或螯合劑、有機溶劑及其類似物。本發明之洗淨及 殘餘物移除組合物尤其適合用於洗淨微電子物基板。 【實施方式】 本發明之含水洗淨組合物之含水量以該組合物重量計一 般為約60%至約99.5%，較佳為約75%至約99%，更佳為約 80%至約98%，且最佳為約83%至約98%。 本發明之含水洗淨組合物含有次磷酸根及/或亞磷酸根 離子及銨離子。該次磷酸根/亞磷酸根及銨/第四銨離子較佳 由亞磷酸銨鹽提供，其用量以該組合物重量計為約〇5%至 約40%，一般為約1。/❶至約25%，較佳為約2。/。至約2〇%，更 佳為約2%至約17。/。，且在某些情況下為h8%至2〇%。該等 次磷酸根/亞構酸根及錄離子亦可由適於提供該等離子之 200536936 其他組份提供，例如，由次磷酸及/或 ^ 納細a或第四鍵發較佳為四炫基兹趣二組= 供。不論如何該等組份之組合將足以向本發明之洗淨組合 物中提供與上文所述由錢鹽所提供之量相等之次鱗酸根/ 亞麟酸根離子及錄/第四銨離子。意即該等提供次鱗酸根/ 亞碌酸根離子及銨/第四銨離子之組份總共構成以該組合 物重量計之約〇.5%至約40%，較佳為約1%至約25%，更佳 為約2%至約20%，且最佳為約2%至約17%。 在一較佳實施例中，本發明之含水洗淨組合物亦含有來 自任意適當氟化物之氟離子，如例如來自氣化氣、氣化四 烷基銨：氟化四甲基銨及氟化四丁基銨，&氟化銨。其他 適當之氟化物例如包括氟硼酸鹽、氟硼酸四丁基銨、六氟 化銘、氟化綈及其類似物。存在於該組合 份之量以該組合物重量計一般為—高至約1〇，= 〇%高至約丨％，較佳以該組合物重量計為約1〇至約5〇〇〇 PPm或0.0〇1%至約㈣，且更佳以該組合物重量計為約 ppm至約 2〇〇〇 ppm或 〇 0〇1%至約 〇 2%。 本發明之含水洗淨組合物亦可且較佳含有一或多種適當 之水溶性有機溶劑。各種有機溶劑中適當之為醇類、多經 基醇類如甘油、二醇類、二醇賴m各相如义甲 基吡咯啶_ (丽P)、i 經燒基I料啶酮如i _(2,乙基 :咬調⑽P)、二甲基甲酿胺（DMF)、二甲基乙酿胺 e)、環丁颯或二甲基亞碾（麵〇)。若需要進一步抑 制紹及/或IS _合金腐㈣可加人該等溶劑以限制該等洗淨 96961.doc 200536936 組“勿之侵襲性及降低金屬尤其為銘或銘合 率。較佳之水溶性有機溶劑為多經基醇如甘油 = 嘻㈣及/幻-經燒基·2_料㈣如 土°比 _(叫該等有機溶劑 f·2,各咬 一 ⑷心用里以0亥組合物重量計為0重晉 %咼至約5 0重量％，鲂佔盔鉍d Θ 里 里里❶季乂佳為約5重量％至約5〇重量％且 約10重量％至約5 〇重量％。 … 本發明之洗淨組合物較佳亦含有氧化劑以提供進— 護免於金屬尤其為銘之腐钱。本發明之洗淨組合物切使 用任意適當之氧化劑，包括（但不限於）過氧化氫、過硫酸 鹽、過鱗酸鹽、次硫酸鹽、次氣酸鹽及其類似物。較佳之 乳化劑為過氧化氫。所使用氧化劑量以該組合物重量計_ 般為〇%高至約5%’較佳為約〇 25%至約5%，更佳為約〇 5% 至3 A ’且最佳為約〇 · 6%至約1 · $ %。 本發明之組合物亦可含有任意適當之水溶性的兩性、非 離子冑離子或陰離子界面活性劑。力口入界面活性劑將降 低該調配物之表面張力且改良待洗淨表面之潤濕性且因此 改良該組合物之洗淨作用。若需要進一步抑制銘腐餘，則 亦叮力入界面’舌性劑以降低紹腐餘速率。適用於本發明之 組合物中的兩性界面活性劑包括甜菜鹼類及磺基甜菜鹼 類，如烷基甜菜鹼 '醯胺基烷基甜菜鹼、烷基磺基甜菜鹼 及醯胺基烷基磺基甜菜鹼；胺基羧酸衍生物類，如兩性甘 月女酸酯、兩性丙酸酯、兩性二甘胺酸酯、及兩性二丙酸酯； 亞胺基二酸類，如烷氧烷基亞胺基二酸或烷氧烷基亞胺基 一酸’氧化胺類，如氧化烷基胺及氧化烷基醯胺基烷基胺； 96961.doc 200536936 石頁酸氟烷酯及兩性氟化烷基及其混合物。該等兩性界面活 性劑較佳為可可醯胺基丙基甜菜驗、可可醯胺基丙基二甲 基甜菜鹼、可可醯胺基丙基羥磺基甜菜鹼、辛醯基兩性二 丙酸酯、可可醯胺基二丙酸酯、可可兩性丙酸酯、丙酸可 可兩性經乙酯、異癸基氧丙基亞胺基二丙酸、月桂基亞胺 基二丙酸醋、氧化可可醯胺基丙胺及氧化可可胺及兩性氟 化烧基。適用於本發明之組合物中之非離子界面活性劑包 括炔系二醇、乙氧基化炔系二醇、氟化烷基烷氧基化物、 氟化烷基酯、氟化聚氧化乙烯烷醇、多羥基醇脂肪酸酯、 聚氧化乙烯單烷基醚、聚氧化乙烯二醇、矽氧烷型界面活 性劑，及伸烷基二醇單烷基醚。該等非離子界面活性劑較 佳為炔系二醇或乙氧基化炔系二醇。適用於本發明之組合 物中之陰離子界面活性劑包括羧酸酯、肌氨酸冰醯基酯、 磺酸酯、硫酸酯、及正磷酸單酯及二酯如磷酸癸酯。該等 陰離子界面活性劑較佳為不含金屬之界面活性劑。適用於 本發明之組合物中之陽離子界面活性劑包括乙氧基化胺、 二烷基二甲基銨鹽、二烷基嗎啉鑌鹽、烷基节基二甲基銨 鹽、烷基二甲基銨鹽，及院基吡σ定鏽鹽。該等陽離子界面 活性劑較佳為不含鹵素之界面活性劑。Α其適當之界面活 性劑實例包括（但不限於）3,5-二甲基小己炔醇 (Wynol-61)、乙氧基化2,4,7,9_四甲基_5_癸块_4,7-二醇 (Surfynol-465)、聚四氟乙烯十六氧丙基甜菜鹼 (cetoxypropylbetaine)(Zonyl FSK)> Zonyl FSH^ Triton χ.1〇〇 即辛基苯氧基聚乙氧基乙醇，及其類似物。該界面活性劑 96961.doc 200536936 存在的量以該組合物重量計一般為〇至約5重量％，較佳為 0.001至約3重量％。 本發明之含水洗淨組合物亦可視情況含有其它組份，包 括（但不限於）微電子物洗淨劑組合物中所採用之腐蝕抑制 劑及類似無腐蝕性組份。該等化合物可包括兒茶酚、間苯 二紛、沒食子酸、沒食子酸丙酯、焦性沒食子酸、對苯二 齡、苯幷三唑衍生物，及多官能羧酸，如檸檬酸、酒石酸、 葡萄糖酸、葡萄糖二酸、甘油酸、草酸、鄰苯二甲酸、順 丁烯二酸、扁桃酸、丙二酸、乳酸及水揚酸。 有機或無機螯合劑或金屬錯合劑並非為必需的，但其提 供了實質性的益處，如例如當其併入本發明之含水洗淨組 合物中時可改良產物之穩定性。適當之螯合劑或錯合劑實 例包括（但不限於）反-Μ-環己烷二胺四乙酸（CyDTA)、乙二 胺四乙酸（EDTA)、錫酸鹽、焦磷酸鹽、亞烷基-二膦酸衍生 物（如乙烧經基-i，i -二膦酸鹽）、含乙二胺、二伸乙基三 胺或三伸乙基四胺官能部分之膦酸鹽[如乙二胺四（亞甲基 膦酸）（EDTMP)、二伸乙基三胺五（亞甲基膦酸）、三伸乙基 胺/、（亞甲基膦酸）]。該螯合劑存在於該組合物中的量以 該組合物重量計為〇至約5重量❹/〇,較佳為約0.1至約2重量 %。當各種膦酸鹽之金屬螯合劑或錯合劑，如乙二胺四（亞 甲基膦酸）(EDTMP)與氧化劑於酸性及鹼性條件下組合時 其大大改良本發明之洗淨組合物之穩定性，且因此其一般 係較佳的。 在本發明之一較佳實施例中，該洗淨組合物包含水及次 96961.doc 200536936 磷酸錄，尤其為98重量％效击 中之2重量％次石粦酸銨。本發明 之另一較佳洗淨組合物#人， 匕3水、次磷酸錄及氫氟酸之組合 物。本發明之洗淨组合 ^ 、 物之另一較佳實施例包含水、次磷 酸錄、氫敦酸、甘油；5备 及過虱化風。另一較佳組合物包含次 磷酸及/或亞磷酸、氫氧化銨、及水。 本4月之組合物、其於洗淨微電子物基板之用途及其無 金屬腐蝕之特性由(但不限於)下列實例蘭明。 實例1-5 將次稱酸銨、去離子水及5〇:1HF混合得到用於提供本發 明之洗淨組合物之2重量％次磷酸銨、98重量％水及1〇〇啊 氟離子的溶液。溶液之pH值為43。將一定量的該溶液置放 於一燒杯中且使其達到45t。將帶有TiN/A1/TiN/pTE〇s層 之圖案化矽晶圓樣品於該經加熱之溶液中置放規定的時 間，此後移除該等樣品，用去離子水漂洗並用氮氣吹乾。 拍攝該等經洗淨之晶圓樣品之掃描電子顯微圖（sem)且關 於灰分移除及鋁金屬腐蝕之程度進行評估。表丨中之結果表 明本發明之組合物之洗淨及相對無腐蝕性質。 表1 實例編號 浸沒時間（min) ~ j分移除％ 100 崔呂腐餘A/miti 1058 1 1.0 ~ 2 1.5 100 3 2.0 100 ____ 4 2.5 100 _L〇84 5 3.0 100 __i〇33 實例6-10 實例1-5中所使用之溶液亦用於下列實例6·1〇中。實例 96961.doc -13- 200536936 1 〇中所使用之晶圓為實例1 -5中所使用類型之晶圓，其帶 有穿過PTEOS圖案化停留於下層TiN頂部上之通道。該洗淨 浴液與實例1-5之洗淨溶液相同。將該等晶圓於經加熱（45。〇 之溶液中置放規定的時間，此後移除該等晶圓，經去離子 水漂洗並用氮氣吹乾。拍攝該等經洗淨之晶圓樣品之掃描 電子顯微圖（SEM)且關於灰分移除及鋁金屬腐蝕之程度進200536936 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for cleaning a microelectronic substrate with a rubidium, and an aqueous composition after cleaning and / or a photoresist ash residue. The composition of the present invention provides enhanced protection to metals when the microelectronic substrates are subjected to cleaning and subsequent water rinsing, i.e., inhibits corrosion. [Prior art] Many photoresist strippers and residue removers have been proposed for use in the field of microelectronics as downstream or end of manufacturing line cleaners. A photoresist film is deposited on the substrate material during the process, and the circuit design is subsequently developed. Hai film. After baking, the exposed resist photoresist developer is removed, and the resulting image is transferred to the underlying layer of dielectric or metal by using the name of the remaining gas or chemical solution. Materially. Etchant gas or chemical solution of the etchant selectively invades the unprotected area of the substrate. The result of the electro-hydraulic etching process is that the by-products of the photoresist and the etched material are deposited on the substrate as residues. And around the opening on the photoresist or on the side wall. In addition, after the etching step is terminated, the resist mask must be removed from the protected area of the substrate for the next process operation. This can be achieved through a plasma ashing step using a suitable plasma ashing gas or wet chemical stripping agent. It was found that although the cleaning composition is suitable for removing the resist mask without disadvantages, for example, corrosion, etching or passivation, metal circuits have also proven to be problematic. Due to the increase in the integration of microelectronics manufacturing and the reduction in the size of patterned microelectronics devices, it is appropriate to provide appropriate photoresist stripping and cleaning with appropriate peeling and cleaning characteristics without other adverse effects96961.doc 200536936 ^ A σ objects are even more difficult. In the field of semiconductors and flat panel displays (FPDs), especially when metals such as titanium and tungsten and alloys are selected for use, the problem of photoresist stripping, residue removal and water> metal rot in the washing process is a serious problem. defect. '' A typical residue remover for microelectronics applications can be an alkali-containing composition that includes a polar = organic solvent blended with organic or hydroxylamines and other solvating agents in an attempt to mitigate metal and dielectric attack Or corrosion. Amines and hydroxylamines have been shown to enhance photoresist and residue removal in solvent blends. However, these alkaline ash residue removal formulations experience carbon dioxide absorption from the air, which in most cases shortens the effective plating time of the detergent solution. In addition, the alkaline detergent compositions work relatively slowly and require the substrates to be placed in the cleaning solutions at elevated temperatures for an extended period of time. In addition, rinsing with water after using this type of remover can generate a strong alkaline aqueous solution, which can cause considerable loss of metal self-patterned circuits. ^ It is necessary to perform an intermediate rinse between the washing / stripping step and the water rinse. This intermediate rinsing usually uses isopropanol, adding unnecessary time, safety considerations, environmental impacts and costs to the process. Therefore, there is a need for a stripping and cleaning composition for photoresist and residues, which can completely remove the etchant and / or ash residues from the microelectronics substrate. In particular, it is required that these do not cause any significant metal corrosion. Detergent and residue removal composition. [Summary of the Invention] The present invention provides an aqueous cleaning composition for cleaning microelectronic substrates, which can basically completely clean the substrates and does not substantially generate metal corrosion for the metal elements of the substrates. 96961.doc 200536936 Money, and the washing time is relatively short compared to the washing time required for the alkali-containing washing composition of the prior art, and is ordered at a relatively low temperature. The present invention also provides a method for cleaning microelectronic substrates using these aqueous cleaning compositions, specifically FPD microelectronic substrates, and does not generate any significant metal corrosion to the metal components of the microelectronic substrates. The aqueous cleaning composition of the present invention comprises at least one of (a) water, (b) ammonium or a fourth ammonium ion, and (c) hypophosphite (H2P〇2 ·) or phosphite (Hp〇32 ·) At least one of ions. It should be understood that ammonium and fourth ammonium ions may be present in the composition of the present invention, and hypophosphite and phosphite ions may also be present in the composition of the present invention. In another embodiment of the present invention, the cleaning composition of the present invention preferably also contains fluoride ions. The cleaning composition of the present invention may optionally contain other components in the composition, such as, for example, a surfactant, a metal complexing agent or a chelating agent, an organic solvent, and the like. The cleaning and residue removing composition of the present invention is particularly suitable for cleaning microelectronic substrates. [Embodiment] The water content of the aqueous cleaning composition of the present invention is generally about 60% to about 99.5%, preferably about 75% to about 99%, more preferably about 80% to about 99% by weight of the composition. 98%, and most preferably about 83% to about 98%. The aqueous cleaning composition of the present invention contains hypophosphite and / or phosphite ions and ammonium ions. The hypophosphite / phosphite and ammonium / fourth ammonium ions are preferably provided by ammonium phosphite, and the amount of the hypophosphite / phosphite and ammonium / fourth ammonium ions is from about 05% to about 40%, usually about 1 based on the weight of the composition. / ❶ to about 25%, preferably about 2. /. To about 20%, more preferably about 2% to about 17. /. , And in some cases h8% to 20%. The hypophosphite / acidite and recording ion can also be provided by other components suitable for providing the ion, such as 200536936, for example, hypophosphorous acid and / or ^ nano-a or the fourth bond is preferably tetrazine Fun two group = for. In any case, the combination of these components will be sufficient to provide the cleaning composition of the present invention with the same amounts of subscale linate / linate ion and quaternary ammonium ion provided by the salt as described above. That is to say, the components that provide hyposquamate / sulfonate and ammonium / fourth ammonium ions constitute a total of about 0.5% to about 40% by weight of the composition, preferably about 1% to about 25%, more preferably about 2% to about 20%, and most preferably about 2% to about 17%. In a preferred embodiment, the aqueous cleaning composition of the present invention also contains fluoride ions from any suitable fluoride, such as, for example, from gasification gas, gasified tetraalkylammonium: tetramethylammonium fluoride and fluorinated Tetrabutylammonium, & ammonium fluoride. Other suitable fluorides include, for example, fluoborate, tetrabutylammonium fluoborate, hexafluoroammonium, rhenium fluoride, and the like. The amount present in the composition is generally up to about 10% by weight of the composition, = 0% up to about 丨%, preferably from about 10 to about 5000 ppm by weight of the composition. Or from 0.01% to about 200%, and more preferably from about ppm to about 2000ppm or from 0.001% to about 0.02% by weight of the composition. The aqueous cleaning composition of the present invention may also and preferably contain one or more suitable water-soluble organic solvents. Among the various organic solvents, suitable are alcohols, polyacryl alcohols such as glycerol, glycols, glycols, and other phases such as methylpyrrolidine (P), i-pyridinone such as i (2, Ethyl: bite-adjusted P), dimethyl methylamine (DMF), dimethyl ethyl amine e), cyclobutane, or dimethylimine (surface 0). If further suppression of Shao and / or IS _ alloy corrosion can be added to these solvents to limit the cleaning 96961.doc 200536936 group "Do not be aggressive and reduce the metal is especially inscription or inscription rate. Better water solubility The organic solvents are polyacryl alcohols such as glycerol = glutamate and / magnesium-pyrrolidone · 2 _ materials such as soil ° ratio _ (referred to as these organic solvents f · 2, each bite one by one) Based on the weight of the material, it is 0% by weight to about 50% by weight, and 鲂 accounts for bismuth of the helmet d Θ 里 里 里 ❶❶ 乂 is about 5% to about 50% by weight and about 10% to about 50% by weight. %.… The cleaning composition of the present invention preferably also contains an oxidant to provide protection from metal, especially rotten money. The cleaning composition of the present invention uses any suitable oxidant, including (but not limited to) Hydrogen peroxide, persulfate, perscale, hyposulfite, hypooxynate, and the like. The preferred emulsifier is hydrogen peroxide. The amount of oxidant used is generally 0% by weight of the composition Up to about 5% 'is preferably about 0.025% to about 5%, more preferably about 5% to 3A' and most preferably about 0.6% to about 1. $%. The composition of the present invention may also contain any suitable water-soluble amphoteric, non-ionic ammonium ions or anionic surfactants. The incorporation of surfactant into the mouth will reduce the surface tension of the formulation and improve the surface of the surface to be cleaned. Wettability and therefore improve the cleaning effect of the composition. If further suppression of rotten residues is required, it is also important to enter the interface 'tongue agent to reduce the rate of rotten residues. Suitable for the amphoteric interface in the composition of the present invention Active agents include betaines and sulfobetaines, such as alkyl betaines' amido alkyl betaines, alkyl sulfo betaines and amido alkyl sulfo betaines; amino carboxylic acid derivatives Class, such as amphoteric glycinate, amphoteric propionate, amphoteric diglycinate, and amphoteric dipropionate; iminodiacids, such as alkoxyalkyliminodiacid or alkoxyalkyl Imine monoacid 'amine oxides, such as alkyl oxide amines and alkyl sulfonium alkyl amine oxides; 96961.doc 200536936 fluorane alkyl oxalate and amphoteric fluorinated alkyl and mixtures thereof. These amphoteric interfaces The active agent is preferably cocoa, aminopropyl beet test, cocoa Amidopropyl dimethyl betaine, cocoa aminopropylhydroxysulfobetaine, octyl amphoteric amphoteric dipropionate, cocoa amidino dipropionate, cocoa amphoteric propionate, propionic acid cocoa Ethyl ester, isodecyloxypropylimine dipropionic acid, laurylimino dipropionate, cocoamine propylamine and cocoamine oxidized and amphoteric fluorinated cyanide. Suitable for the composition of the present invention Non-ionic surfactants include acetylene glycols, ethoxylated alkyne glycols, fluorinated alkyl alkoxylates, fluorinated alkyl esters, fluorinated polyoxyethylene alkanols, polyhydric alcohol fatty acids Esters, polyoxyethylene monoalkyl ethers, polyoxyethylene glycols, siloxane-type surfactants, and alkylene glycol monoalkyl ethers. These nonionic surfactants are preferably acetylene glycols or Ethoxylated alkyne glycol. Anionic surfactants suitable for use in the compositions of the present invention include carboxylic acid esters, sarcosinyl behenyl esters, sulfonate esters, sulfate esters, and orthophosphate mono- and diesters such as decyl phosphate. These anionic surfactants are preferably metal-free surfactants. Cationic surfactants suitable for use in the compositions of the present invention include ethoxylated amines, dialkyldimethylammonium salts, dialkylmorpholine phosphonium salts, alkylbenzyldimethylammonium salts, and alkyldiamines. Methyl ammonium salts, and sylpyridine sigma dine rust salts. These cationic surfactants are preferably halogen-free surfactants. Α Examples of suitable surfactants include (but are not limited to) 3,5-dimethyl small hexynol (Wynol-61), ethoxylated 2,4,7,9_tetramethyl_5_dec Block_4,7-diol (Surfynol-465), polytetrafluoroethylene cetoxypropylbetaine (Zonyl FSK) > Zonyl FSH ^ Triton χ. 100 is octylphenoxy poly Ethoxyethanol, and its analogs. The surfactant 96961.doc 200536936 is generally present in an amount of 0 to about 5% by weight, preferably 0.001 to about 3% by weight based on the weight of the composition. The aqueous cleaning composition of the present invention may optionally contain other components, including (but not limited to) corrosion inhibitors and similar non-corrosive components used in microelectronic detergent compositions. These compounds may include catechol, isophthalic acid, gallic acid, propyl gallate, pyrogallic acid, terephthalic acid, benzotriazole derivatives, and polyfunctional carboxylic acids. , Such as citric acid, tartaric acid, gluconic acid, gluconic acid, glyceric acid, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, lactic acid and salicylic acid. Organic or inorganic chelating agents or metal complexing agents are not necessary, but they provide substantial benefits such as, for example, improved product stability when incorporated into the aqueous cleaning composition of the present invention. Examples of suitable chelating or complexing agents include, but are not limited to, trans-M-cyclohexanediaminetetraacetic acid (CyDTA), ethylenediaminetetraacetic acid (EDTA), stannates, pyrophosphates, alkylene- Bisphosphonic acid derivatives (such as ethylene glycol-i, i-bisphosphonates), phosphonates containing ethylenediamine, diethylene triamine or triethylene tetramine functional moieties [such as ethylene diethylene Amine tetrakis (methylenephosphonic acid) (EDTMP), diethylenetriaminepenta (methylenephosphonic acid), triethyleneamine /, (methylenephosphonic acid)]. The chelating agent is present in the composition in an amount of 0 to about 5 weight% / 0, preferably about 0.1 to about 2 weight% based on the weight of the composition. When a variety of phosphonate metal chelating agents or complexing agents, such as ethylenediamine tetra (methylenephosphonic acid) (EDTMP), are combined with oxidants under acidic and alkaline conditions, it greatly improves the cleaning composition of the present invention. Stability, and therefore it is generally better. In a preferred embodiment of the present invention, the cleaning composition comprises water and phosphoric acid 96961.doc 200536936, especially 2% by weight of ammonium hypophosphite which is 98% by weight. Another preferred cleaning composition of the present invention is a combination of human, water, hypophosphorous acid and hydrofluoric acid. Another preferred embodiment of the cleaning composition of the present invention includes water, hypophosphorous acid, hydrotonic acid, glycerin; 5 preparations, and insecticidal wind. Another preferred composition comprises hypophosphorous acid and / or phosphorous acid, ammonium hydroxide, and water. The composition of this April, its use in cleaning microelectronic substrates, and its non-metal corrosion characteristics are clarified by (but not limited to) the following examples. Examples 1-5 A mixture of hypoxic ammonium acid, deionized water, and 50: 1HF was used to obtain 2% by weight of ammonium hypophosphite, 98% by weight of water, and 100% fluoride ion for providing the cleaning composition of the present invention. Solution. The pH of the solution was 43. A certain amount of this solution was placed in a beaker and allowed to reach 45t. Samples of the patterned silicon wafer with the TiN / A1 / TiN / pTE0s layer were placed in the heated solution for a specified time, after which the samples were removed, rinsed with deionized water, and dried with nitrogen. Scanning electron micrographs (sem) of these cleaned wafer samples were taken and evaluated for the extent of ash removal and aluminum metal corrosion. The results in Table 丨 show the cleaning and relatively non-corrosive properties of the composition of the present invention. Table 1 Example number Immersion time (min) ~ j minutes removal% 100 Cui Luyu Yu A / miti 1058 1 1.0 ~ 2 1.5 100 3 2.0 100 ____ 4 2.5 100 _L〇84 5 3.0 100 __i〇33 Example 6-10 The solutions used in Examples 1-5 were also used in the following Example 6.10. The wafer used in Example 96961.doc -13-200536936 10 is the type of wafer used in Example 1-5 with a channel patterned through PTEOS to stay on top of the lower TiN. This washing bath was the same as the washing solution of Example 1-5. The wafers were placed in a heated (45.0% solution) for a specified period of time, after which the wafers were removed, rinsed with deionized water and blown dry with nitrogen. Photographs of the washed wafer samples Scanning electron micrograph (SEM) and progress on the extent of ash removal and aluminum metal corrosion
行孑估。表2中報導其結果，顯示當本發明之組合物用於更 久洗淨時期時其侵襲性增加。 表2 實例編號 浸沒時間（min) 灰分移除％ 鋁腐蝕％ 6 2.0 3 0 7 8 2.5 1---- 40 0 3 ·〇 50 〇 9 3.5 90 20 10 40 100 80 實例11 -12Line estimation. The results are reported in Table 2 and show that the composition of the present invention has an increased aggressiveness when used for a longer washing period. Table 2 Example number Immersion time (min) Ash removal% Aluminum corrosion% 6 2.0 3 0 7 8 2.5 1 ---- 40 0 3 · 〇 50 〇 9 3.5 90 20 10 40 100 80 Example 11 -12
實例11及12中使用與實例1-5中所使用之同樣類型之圖 案化晶圓。所使用之洗淨溶液為實例卜5中所使用之洗淨溶 T但需於其中加入甘油’甘油的量構成該組合物之約10重 量％。該溶液之pH值仍為4.3。將該等晶圓於經加熱⑷。〇 之溶液中置放規定的時間’此後移除該等晶圓、經去離子 水漂洗並用氮氣吹乾。拍攝該等經洗淨之晶圓樣品之掃描 電子顯微圖（SEM)且關於灰分移除及|g金屬腐敍之程度進 仃。平估。表3中報導其結果且顯示鋁腐蝕進一步減少約 96961.doc -14- 200536936 表3 實例編號 浸沒時間（min) 灰分移除％ 銘腐ϋ A/min 11 2.5 100 952 12 3.0 100 903 實例13-14 實例13-14中使用帶有與實例6-1 〇中所使用之同樣類型通 道之晶圓。所使用之洗淨溶液為實例丨丨·丨2中所使用之洗淨 溶液。將該等晶圓於經加熱（45°C )之溶液中置放規定的時 間，此後移除該等晶圓、經去離子水漂洗及並用氮氣吹乾。 拍攝该等經洗淨之晶圓樣品之掃描電子顯微圖（SEM)且關 於灰分移除及IS金屬腐姓之程度進行評估。表4中報導其結 果且顯示當該組合物為如表2中先前結果所揭示之更具侵 襲性之洗淨劑時甚至於延長洗淨時期下鋁腐蝕的進一步顯 著減少。 表4 實例編號 浸沒時間（min) 灰分移除％ 鋁腐蝕％ 13 3.5 100 20 14 4.0 100 20 實例15-16 實例1 5中所使用之晶圓與實例i _ 5中所描述之晶圓相同 且實例16中所使用之帶有通道之晶圓與實例6_1()中所描述 之晶圓相同。所使用之洗淨組合物為先前實例中所描述之 類型但需加入過氧化氫。該洗淨溶液包含18重量％次磷酸 I 88·4重量％水' 8·8重量％甘油、〇 6重量％過氧化氣及稍 低於⑽ppm之氟離子且其ρΗ值為43。將該等晶圓於經加 熱（45°C)之溶液巾置放規定的時間，此後移除該等晶圓、經 96961.doc -15- 200536936 去離子水漂洗及並用氮氣吹乾。拍攝該等經洗淨之晶圓樣 品之掃描電子顯微圖（SEM)且評估關於灰分移除及鋁金屬 腐餘之程度。表5中報導其結果且顯示對於兩種類型之晶圓 而言鋁腐蝕均進一步顯著減少。 表5 實例編號 浸沒時間 (min) 灰分移除 % 紹腐敍 A/min 鋁腐蝕 % 15 1.5 100 840 16 3.0 100 - 0 實例17 製備具有下列組成之本發明之組合物：1〇〇 g去離子水、 25.0 g 1.0%氫氟酸、4.27 g 24.96%氫氧化四甲銨水溶液、 20.0 g甘油、2.0 g單水合次磷酸納（來自Alfa Aesar)及0.08 重量％ Triton X-1 〇〇界面活性劑。室溫下該組合物之pH值約 為6.0。將一具有PTEOS/TiN/A1-0.5〇/o Cu層之晶圓樣品電漿 灰化以在通道蝕刻後移除表體光阻劑，該晶圓樣品帶有穿 過PTEOS圖案化停留於下層TiN頂部上之通道。將將該晶圓 於25 C下於該洗淨溶液中處理2〇分鐘。縱橫比為5:1(高度： 寬度）之0· 18微米寬通道之SEM橫截面檢測顯示該等通道為 完全洗淨且不含殘餘物。 實例18 製備具有下列組成之本發明之洗淨組合物：1〇〇 〇〇 g去離 子水、25.54 g 1%氫氟酸水溶液、5·96 g 25.08。/。氫氧化四甲 銨水溶液、60.00 g甘油及2.00 g次磷酸銨（97%來自Fluka)。 25°C下該組合物之pH值約為8·36。將帶有TiN/A1_〇.5% Cu/TiN/Ti/旋塗式玻璃（sog)層之具有1微米寬特徵之圖案化 96961.doc -16 - 200536936 金屬導線晶圓樣品電漿灰化以在金屬餘刻後移除表體光阻 劑。將該晶圓於30°C下於洗淨組合物中處理2分鐘。SEM檢 測顯示99.5%殘餘物移除且觀察不到金屬腐蝕。 實例19-21 藉由將次磷酸銨與去離子水混合來提供僅包含次磷酸銨 及水之溶液從而製備本發明之洗淨組合物。將具有 TiN/Al/TiN/PTEOS層之圖案化矽晶圓樣品於經加熱之洗淨 組合物溶液中置放1 5分鐘，此後移除該等樣品，經去離子 水漂洗並用氮氣吹乾。隨後評估該等經洗淨晶圓之灰分殘 餘物移除（0 =無移除至10 = 1〇0%移除）及鋁腐蝕（〇 =無腐 餘至10 =嚴重腐餘）。次麟酸錢百分比、溶液之pH值、該等 晶圓所置放之經加熱溶液之溫度及鋁腐蝕及灰分移除結果 陳述於表6中。 表6 實例編號 次麟酸錢 % pH值 溫度 °C 鋁腐蝕 灰分殘餘 物移除 19 1.6 3 45 0 10 — 20 3.2 3 25 1 10 21 Γ 2.4 L_4__ 35 lzzzzzj 1 V 10 實例22-27 藉由將次磷酸與亞磷酸、氫氧化銨及去離子水混合來製 備本發明之洗淨組合物。將具有TiN/A1/TiN/pTE〇s層之圖 案化矽晶圓樣品於加熱至451之洗淨組合物溶液中置放15 刀鐘此後移除该等樣品，經去離子水漂洗並用氮氣吹乾。 隨後評估該等經洗淨晶圓之灰分殘餘物移除（〇=無移除至 1〇=1〇〇%移除）及鋁腐蝕（0=無腐蝕至1〇=嚴重腐蝕）。任 96961.doc 200536936 一亞鱗酸鹽百分比 如表7中所示。 溶液之PH值及銘腐餘及灰分移除結果 表7Examples 11 and 12 used patterned wafers of the same type as those used in Examples 1-5. The cleaning solution used was the cleaning solution used in Example 5 but the amount of glycerol 'glycerol needed to constitute it was about 10% by weight of the composition. The pH of the solution was still 4.3. The wafers are heated. The solution was left in the solution for a prescribed time ′, after which the wafers were removed, rinsed with deionized water, and dried with nitrogen. Scanning electron micrographs (SEM) of these cleaned wafer samples were taken with regard to the extent of ash removal and | g metal corrosion. Flat estimate. The results are reported in Table 3 and show that the aluminum corrosion is further reduced by approximately 96961.doc -14- 200536936 Table 3 Example No. Immersion Time (min) Ash Removal% Ming Corrosion A / min 11 2.5 100 952 12 3.0 100 903 Example 13- 14 Examples 13-14 used wafers with the same type of channels as used in Example 6-10. The washing solution used was the washing solution used in Example 丨 丨 2. The wafers were placed in a heated (45 ° C) solution for a specified period of time, after which the wafers were removed, rinsed with deionized water, and dried with nitrogen. Scanning electron micrographs (SEM) of these cleaned wafer samples were taken and evaluated for the extent of ash removal and IS metal rot. The results are reported in Table 4 and show a further significant reduction in aluminum corrosion even when the composition is a more aggressive detergent as revealed by the previous results in Table 2 even with extended cleaning periods. Table 4 Example number Immersion time (min) Ash removal% Aluminum corrosion% 13 3.5 100 20 14 4.0 100 20 Examples 15-16 The wafers used in Example 1 5 are the same as the wafers described in Example i _ 5 and The wafer with channels used in Example 16 is the same as the wafer described in Example 6_1 (). The cleaning composition used was of the type described in the previous examples but required the addition of hydrogen peroxide. The cleaning solution contained 18% by weight of hypophosphorous acid I 88.4% by weight of water '8.8% by weight of glycerol, 06% by weight of peroxide gas, and fluorine ions slightly lower than ⑽ppm, and had a ρΗ value of 43. The wafers were placed in a heated (45 ° C) solution towel for a specified period of time, after which the wafers were removed, rinsed with 96961.doc -15- 200536936 deionized water, and dried with nitrogen. Scanning electron micrographs (SEM) of these cleaned wafer samples were taken and evaluated regarding the extent of ash removal and aluminum metal corrosion. The results are reported in Table 5 and show further significant reductions in aluminum corrosion for both types of wafers. Table 5 Example number Immersion time (min) Ash removal% Shao A / min Aluminum corrosion% 15 1.5 100 840 16 3.0 100-0 Example 17 A composition of the present invention having the following composition was prepared: 100 g deionized Water, 25.0 g of 1.0% hydrofluoric acid, 4.27 g of 24.96% tetramethylammonium hydroxide aqueous solution, 20.0 g of glycerol, 2.0 g of sodium hypophosphite monohydrate (from Alfa Aesar) and 0.08% by weight of Triton X-1 〇〇 surfactant . The pH of the composition at room temperature was about 6.0. A wafer sample with a PTEOS / TiN / A1-0.50 / o Cu layer was plasma ashed to remove the surface photoresist after channel etching. The wafer sample was patterned through PTEOS and remained at the lower layer. Channel on top of TiN. The wafer was processed in the cleaning solution at 25 C for 20 minutes. SEM cross-sectional inspection of 0. 18 microns wide channels with an aspect ratio of 5: 1 (height: width) showed that the channels were completely cleaned and free of residue. Example 18 A cleaning composition of the present invention having the following composition was prepared: 1000 g of deionized water, 25.54 g of a 1% aqueous hydrofluoric acid solution, and 5.96 g of 25.08. /. Aqueous tetramethylammonium hydroxide solution, 60.00 g glycerol and 2.00 g ammonium hypophosphite (97% from Fluka). The pH of the composition at 25 ° C was about 8.36. Patterning of 1 micron wide features with TiN / A1_〇.5% Cu / TiN / Ti / scoated glass (sog) layer96961.doc -16-200536936 Plasma ashing of metal wire wafer samples In order to remove the surface photoresist after the metal remains. The wafer was processed in the cleaning composition at 30 ° C for 2 minutes. SEM inspection showed that 99.5% of the residue was removed and no metal corrosion was observed. Examples 19-21 The cleaning composition of the present invention was prepared by mixing ammonium hypophosphite with deionized water to provide a solution containing only ammonium hypophosphite and water. A patterned silicon wafer sample having a TiN / Al / TiN / PTEOS layer was placed in a heated cleaning composition solution for 15 minutes, after which the samples were removed, rinsed with deionized water, and dried with nitrogen. The washed wafers were then evaluated for ash residue removal (0 = no removal to 10 = 100% removal) and aluminum corrosion (0 = no corrosion to 10 = severe corrosion). The percentage of hypochlorous acid, the pH value of the solution, the temperature of the heated solution placed on these wafers, and the results of aluminum corrosion and ash removal are stated in Table 6. Table 6 Example No. Phosphonic acid% pH temperature ° C Aluminum residue removal from corrosion 19 1.6 3 45 0 10 — 20 3.2 3 25 1 10 21 Γ 2.4 L_4__ 35 lzzzzzj 1 V 10 Examples 22-27 Hypophosphorous acid is mixed with phosphorous acid, ammonium hydroxide, and deionized water to prepare the cleaning composition of the present invention. A patterned silicon wafer sample with a TiN / A1 / TiN / pTE0s layer was placed in a cleaning composition solution heated to 451 for 15 knife minutes, and then the samples were removed, rinsed with deionized water and blown with nitrogen. dry. The washed wafers were then evaluated for ash residue removal (0 = no removal to 10 = 100% removal) and aluminum corrosion (0 = no corrosion to 10 = severe corrosion). Ren 96961.doc 200536936 The percentage of linolenic acid is shown in Table 7. PH value of solution, residues and ash removal results Table 7
藉由僅將亞碟酸、氫氧化錢及去離子水混合來製備本發 ^之洗淨組合物。將具有TiN/Al/TiN/PTEOS層之圖案化石夕 晶圓樣品於加熱至45〇c之洗淨組合物溶液中置放Η分鐘， 此後移除該等樣品，經去離子水漂洗並用氮氣吹乾。隨後 評估該等經洗淨晶圓之灰分殘餘物移除（〇=無移除至1〇 = 100%移除）及鋁腐蝕（〇=無腐蝕至10=嚴重腐蝕卜亞磷酸 百分比、溶液之pH值，及鋁腐蝕及灰分移除結果如表8中所 示。 表8 實例編號 亞磷酸％ NH4OH % pH值 鋁腐蝕 灰分殘餘物移除 28 1 0.1 1·3 6 10 29 1 0.5 5.6 0 10 30 2 0.4 3.4 4 10 31 2 0.9 4.5 1 10 32 2 1.4 6.0 0 10 33 6 2.7 6 10 34 6 4.3 6.0 2 卜 10 實例35-40 藉由將亞構酸（最終濃度為2%)、去離子水，及選擇達成 96961.doc -18- 200536936 約pH =4.5之強鹼混合以製備本發明之洗淨組合物。該等鹼 為··氫氧化四甲銨（TMAH)、氫氧化四乙銨（TEAH)、氫氧化 四丙銨（TPAH)、氫氧化四丁銨（TB AH)、氫氧化十六烷基三 甲基銨（CTMAH)，及氫氧化四乙醇銨（TEtOHAH)。將具有The washing composition of the present invention is prepared by mixing only acetic acid, sodium hydroxide, and deionized water. Samples of the patterned fossil wafer with a TiN / Al / TiN / PTEOS layer were placed in a cleaning composition solution heated to 45 ° C for Η minutes, after which the samples were removed, rinsed with deionized water and blown with nitrogen. dry. The washed wafers were then evaluated for ash residue removal (0 = no removal to 10 = 100% removal) and aluminum corrosion (0 = non-corrosive to 10 = severely corroded diphosphorous acid, percentage of solution The pH value, and the results of aluminum corrosion and ash removal are shown in Table 8. Table 8 Example No. Phosphorous acid% NH4OH% pH value Aluminum residue removal from ash 28 1 0.1 1 · 3 6 10 29 1 0.5 5.6 0 10 30 2 0.4 3.4 4 10 31 2 0.9 4.5 1 10 32 2 1.4 6.0 0 10 33 6 2.7 6 10 34 6 4.3 6.0 2 Bu 10 Example 35-40 By subliming acid (final concentration 2%), deionization Water and a strong base selected to reach 96961.doc -18- 200536936 are mixed with a strong base having a pH of about 4.5 to prepare the cleaning composition of the present invention. The bases are: Tetramethylammonium hydroxide (TMAH), Tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TB AH), cetyltrimethylammonium hydroxide (CTMAH), and tetraethanolammonium hydroxide (TEtOHAH). Will have
TiN/Al/TiN/PTEOS層之圖案化矽晶圓樣品於加熱至45°C之 洗淨組合物溶液中置放1 5分鐘，此後移除該等樣品，用去 離子水漂洗並用氮氣吹乾。隨後評估該等經洗淨晶圓之灰 分殘餘物移除（0 =無移除至10= 100%移除）及鋁腐蝕（0 = 無腐蝕至10=嚴重腐蝕）。以上鹼之縮寫、溶液之pH值，及 I呂腐#及灰分移除結果如表9中所示。 表9 實例編號 強鹼 pH值 鋁腐蝕 灰分殘餘物移除 35 TMAH 4.5 0 10 36 TEAH 4.5 1 10 37 TPAH 4.5 0 9 38 TBAH 4.6 0 8 39 CTMAH 4.5 0 8 40 TEtOHAH 5.0 0 7 實例41-44 藉由將亞磷酸、氫氧化銨、含或不含兒茶酚，及去離子 水混合以製備本發明之洗淨組合物。將具有 TiN/Al/TiN/PTEOS層之圖案化矽晶圓樣品於加熱至35°C之 洗淨組合物溶液中置放10分鐘，此後移除該等樣品，用去 離子水漂洗並用氮氣吹乾。隨後評估該等經洗淨晶圓之灰 分殘餘物移除（0 =無移除至10 = 100%移除）及鋁腐蝕（0 = 無腐蝕至10=嚴重腐蝕）。如表10中所示之亞磷酸、氫氧化 銨及兒茶齡之百分比、溶液之pH值，及銘腐钱及灰分移除 96961.doc -19- 200536936 μ果顯示本發明之組合物中使用腐蝕抑制化合物如兒茶酚 所獲得之額外有益的結果。 表10 實例編號 亞磷酸鹽％ νη4οη°/〇 兒茶酚％ pH值 鋁腐蝕 灰分殘餘物移f 41 a r\ 0.7 0 3.2 1 10 42 2.5 0.7 3 3.2 0 ίο ' 43 Α Λ ~ 0.3 0 2.2 3 10~- 44 2.5 0.3 3 2.1 1 Ίδ 雖然本發明已於本文中參照其特定實施例進行描述，但 是應瞭解可作出各種改變、修改及變化而不會脫離本文所 揭示之發明概念之實質與範疇。因此，希望將所有該等改 變、修改及變化包含於附加之申請專利之實質與範疇範圍 内。 96961.doc -20-The patterned silicon wafer samples of the TiN / Al / TiN / PTEOS layer were placed in a cleaning composition solution heated to 45 ° C for 15 minutes. Thereafter, the samples were removed, rinsed with deionized water, and dried with nitrogen. . The washed wafers were then evaluated for ash residue removal (0 = no removal to 10 = 100% removal) and aluminum corrosion (0 = no corrosion to 10 = severe corrosion). The abbreviations of the above bases, the pH value of the solution, and the results of the removal of ions and ash are shown in Table 9. Table 9 Example number Strong alkali pH value Aluminum corrosion ash residue removal 35 TMAH 4.5 0 10 36 TEAH 4.5 1 10 37 TPAH 4.5 0 9 38 TBAH 4.6 0 8 39 CTMAH 4.5 0 8 40 TEtOHAH 5.0 0 7 Examples 41-44 Borrow The cleaning composition of the present invention is prepared by mixing phosphorous acid, ammonium hydroxide, with or without catechol, and deionized water. A patterned silicon wafer sample with a TiN / Al / TiN / PTEOS layer was placed in a cleaning composition solution heated to 35 ° C for 10 minutes, after which the samples were removed, rinsed with deionized water and blown with nitrogen dry. The washed wafers were then evaluated for ash residue removal (0 = no removal to 10 = 100% removal) and aluminum corrosion (0 = no corrosion to 10 = severe corrosion). As shown in Table 10, the percentages of phosphorous acid, ammonium hydroxide, and catechin age, the pH value of the solution, and the removal of rot and ash content 96961.doc -19- 200536936 μ show the use of the composition of the present invention Additional beneficial results obtained by corrosion inhibiting compounds such as catechol. Table 10 Example No. Phosphite% νη4οη ° / 〇catechol% pH value Aluminum corrosion ash residue shift f 41 ar \ 0.7 0 3.2 1 10 42 2.5 0.7 3 3.2 0 ί '43 Α Λ ~ 0.3 0 2.2 3 10 ~-44 2.5 0.3 3 2.1 1 Ίδ Although the present invention has been described herein with reference to specific embodiments, it should be understood that various changes, modifications and changes can be made without departing from the essence and scope of the inventive concept disclosed herein. Therefore, it is hoped that all such changes, modifications and variations are included in the substance and scope of the attached patent application. 96961.doc -20-