1334169 9 I 1 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種清洗液，並且特別地，本發明關於一種用 於半導體製程中的金屬防腐蝕清洗液。 【先前技術】 典型的清洗液有去離子水、過氧化氫溶液和稀氨水，它們主 要用於清洗前一程序中殘留液，例如，經化學機械拋光程序後， ^ 金屬表面殘留的拋光液；經過刻餘去強光阻程序後，殘留的去強 光阻液以及經過沉積程序後的殘留液等。其中前一程序殘留液被 清洗後，金屬表面仍然可能存在一些由清洗液引入的有機物殘留 從而影響下一程序製程，或者金屬表面的腐蝕仍然存在，金屬表 面的腐敍會影響金屬表面平坦度品質也使缺陷水準居高不下，從 而降低了產品良率和收益率。 〇此外，一些清洗液已被公開，例如，美國第US2002169088 號專利中的清洗液包含羧酸，含氮化合物和磷酸(carb〇xylic 5 1 ’ phosPhoric acid ’ amine acid)。世界專利第 w〇 2005093031 號專利中的酸性清洗液包含有機酸和含氮抑制劑。世界專利第 WO 2005085408號專利中的鹼性清洗液包含有機酸和含氮抑制 劑。中國專利CN01104317.2中的清洗液包含有機酸，腐蝕抑制 劑’醇胺，多醇類化合物，這些都是關於清洗液或清洗液的使用 =法。美國專利US6147002中的清洗液是關於一種酸性水溶液的 清洗液’其還包含0.5〜5重量％的含氟物質，該清洗液適合於清 洗銅金屬半導體晶片的積體電路元器件。然而，上述專利中的清 洗液，或是含有毒性物質，對環境造成污染；或是清洗效率不夠 =，或是有殘留對後續程序產生不良影響等缺陷；或是清洗使用 範圍窄’例如US64438M專利的清洗液只能夠清洗含銅金屬層的 晶片。 1334169 金層開發丨-種金屬清錄，其械能财效清除 肩表面各種殘留，也能大大降鱗後續程序的干擾。 【發明内容】 、止中是為了解決上述問題，提供—種用於半導體製 ϊ洗ί。除金屬表面各種殘留，大大降低舰續程序的干擾的 以 一根據本發明之一較佳具體實施例的清洗液包含一種載體，…1334169 9 I 1 EMBODIMENT DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a cleaning liquid, and in particular, to a metal anti-corrosion cleaning liquid for use in a semiconductor process. [Prior Art] Typical cleaning solutions are deionized water, hydrogen peroxide solution and dilute ammonia water, which are mainly used for cleaning the residual liquid in the previous procedure, for example, after the chemical mechanical polishing process, ^ the polishing liquid remaining on the metal surface; After the residual photoresist process, residual residual photo-resistance and residual liquid after deposition process. After the previous program residual liquid is cleaned, there may still be some residual organic matter introduced by the cleaning liquid on the metal surface to affect the next process, or the corrosion of the metal surface still exists, and the rot of the metal surface will affect the flatness quality of the metal surface. It also keeps the defect level high, which reduces product yield and profitability. In addition, some cleaning solutions have been disclosed. For example, the cleaning solution of U.S. Patent No. US2002169088 contains a carboxylic acid, a nitrogen-containing compound and phosphoric acid (carb xylic 5 1 'phos Phoric acid ''amine acid). The acidic cleaning solution of the patent of U.S. Patent No. 2005093031 contains an organic acid and a nitrogen-containing inhibitor. The alkaline cleaning solution of the patent of WO 2005085408 contains an organic acid and a nitrogen-containing inhibitor. The cleaning solution in Chinese patent CN01104317.2 contains an organic acid, a corrosion inhibitor, an alcoholamine, a polyol compound, and these are all related to the use of a cleaning solution or a cleaning solution. The cleaning liquid in U.S. Patent No. 6,147,002 is an aqueous acidic cleaning solution which further contains 0.5 to 5% by weight of a fluorine-containing substance suitable for cleaning integrated circuit components of a copper metal semiconductor wafer. However, the cleaning liquid in the above patents either contains toxic substances and causes environmental pollution; or the cleaning efficiency is insufficient = or there are defects such as residues that adversely affect subsequent processes; or the cleaning use range is narrow 'for example, US64438M patent The cleaning solution can only clean the wafer containing the copper metal layer. 1334169 Gold layer development 丨 - a kind of metal inventory, its mechanical energy and efficiency to remove all kinds of residues on the shoulder surface, can also greatly reduce the interference of the follow-up procedures. SUMMARY OF THE INVENTION In order to solve the above problems, the invention provides a semiconductor manufacturing method. In addition to various residuals on the metal surface, the interference of the ship program is greatly reduced. A cleaning fluid according to a preferred embodiment of the present invention comprises a carrier, ...
二效清除金屬表面各種殘留，有效防止金屬表面腐 蝕的有機酸化學添加劑。 該有機酸類化學添加劑為有機紐、有機膦酸或有機績酸以 及它們的形成鹽形成的組合物。 ' 該有機羧酸為檸檬酸、草酸、酒石酸、琥珀酸或馬來酸中的 —種或多種的組合。 一該有機膦酸包含烷基膦酸、苯基膦酸、1_羥基乙烯基^ =膦酸、亞曱基膦酸、乙烯基·二胺_4、亞甲基膦酸、環丁烷基_ 二胺-5-亞曱基膦酸或多氨基多醚基四亞曱基膦酸中的一種或多種 的組合。 該有機磺酸包含曱基磺酸、乙基磺酸、二甲基磺酸或丁基橫 酸内酯中的一種或多種的組合。 、 該含氮氣基酸和它的形成鹽包含甘氨酸、丙氨酸、亮氨酸、 ，亮氨酸、纈氨酸、胱氨酸、半胱氨酸、甲硫氨酸、蘇氨酸、絲 氨酸、苯丙氨酸、酪氨酸、色氨酸、脯氨酸、羥脯氨酸，谷氨 駿、天門冬氨酸、賴氨酸或精氨酸中的一種或多種的組合。 本發明該有機羧酸化學添加劑的重量百分比含量較佳地為 1334169 k ♦ ' 0.05〜5%。 該有機膦酸化學添加劑的重量百分比含量較佳地為〇犯 0.5%。 . 該有機磺酸化學添加劑的重量百分比含量較佳地為〇⑹ 1%。 *、. 該氨基酸化學添加劑的重量百分比含量較佳地為〇 〇5〜5%。A second-effect organic acid chemical additive that removes various residues on the metal surface and effectively prevents corrosion of the metal surface. The organic acid chemical additive is a composition formed by organic nucleus, organic phosphonic acid or organic acid and their salt forming salts. The organic carboxylic acid is a combination of one or more of citric acid, oxalic acid, tartaric acid, succinic acid or maleic acid. An organic phosphonic acid comprising an alkylphosphonic acid, a phenylphosphonic acid, a 1-hydroxyvinyl group = a phosphonic acid, a decylene phosphonic acid, a vinyl diamine _4, a methylene phosphonic acid, a cyclobutane group a combination of one or more of diamine-5-fluorenylene phosphonic acid or polyaminopolyether tetradecylphosphonic acid. The organic sulfonic acid comprises a combination of one or more of mercaptosulfonic acid, ethylsulfonic acid, dimethylsulfonic acid or butyl trasololide. The nitrogen-containing acid and its forming salt comprise glycine, alanine, leucine, leucine, valine, cystine, cysteine, methionine, threonine, serine A combination of one or more of phenylalanine, tyrosine, tryptophan, valine, hydroxyproline, glutamine, aspartic acid, lysine or arginine. The content of the organic carboxylic acid chemical additive of the present invention is preferably 1334169 k ♦ '0.05 to 5% by weight. The content of the organic phosphonic acid chemical additive is preferably 0.5% by weight. The content of the organic sulfonic acid chemical additive is preferably 〇(6) 1% by weight. *,. The content of the amino acid chemical additive is preferably from 5% to 5% by weight.
μ本ίΞϊί洗液還包含pH調節劑、表面活性劑及/或聚合物 金屬防腐抑制劑。 該聚合物金屬防腐抑制劑為聚丙__化合物、丙稀酸類化 合物與苯乙刺共聚化合物、丙烯麵化合物與順谓二酸針的 共聚化合物、丙烯酸類化合物與丙__的共聚化合物、麟酿 基竣酸共雜、丙触=元共㈣或者丙稀酸· 丙稀酸醋-鱗酸-績酸鹽四元共聚物。 該聚合物金屬防腐抑制劑範圍分子量在2,0〇〇〜3,〇〇〇 〇〇〇。 該多聚羧酸及/或其鹽為式〗化合物： ψ Ri γ I | π 〇 " c — CO〇R3」η 小於3的烷基，R3 其中，心、RZ獨自地為氫原子或碳原子數 為 H、K、Na或NH4。 ' 該聚丙烯酸類化合物較佳地為聚丙稀酸。 1334169 30,000 該聚丙烯酸類化合物分子量範圍較佳地為5,〇〇〇 該聚丙烯酸類化合物重量百分比含量輕 5_ppm。 讀佳地為10PPm〜 本發_清洗㈣包含錢雜觀合物絲並三哇“比嗤及/ 或咪哇。 該清洗液還包含含氮雜環化合物為重量百分比含量為〇〜 〇·1% 〇 ® 本發明的清洗液的pH值範圍較佳地為2〜7。 ' 此外，該載體為醇類及/或水。 本發明的清洗液能應用於金屬襯底之清洗。並且，該金屬襯 底為銅、鋁、组、氮化組、鈦、氮化鈦、銀或金。在本發明中， 該β洗液可用於下列程序中：拋光、刻蝕(去強光阻後）、沉積以 及其他保護步驟中。 、 由於該化學添加劑用於本發明的清洗液中，降低對後續程序 鲁 的干擾，大大降低金屬材料的表面點蝕，減低表面腐蝕程度，從 而降低了缺陷，提兩了清洗效率和產品良率，增加了收益率。 本發明的積極進步效果在於：本發明的清洗液能夠大大降低 金屬材料的腐蝕程度從而(1)使缺陷明顯下降；大大改善了金屬 表面的平坦度品質；（3)提高產品良率(4)提高工藝操作視窗。 關於本發明之優點與精神可以藉由以下的發明詳述得到進一 步的瞭解。 【實施方式】 為達到上述有關本發明之範疇，所採用之技術手段及 8 1334169 I 泰 其餘功效’茲舉數個較佳實施例加以說明如下： 實施例1 將含有2%之檸檬酸(Citric acid)和聚丙烯酸（分子量為 5000) lOppm和^為餘j的清洗液(pH=2 4)用於化學機械 拋光液拋光後的^7^^化矽表面。化學機械拋光液拋 光銅金屬的程序為：下壓力l.〇-2.〇psi、拋光盤的轉速 50-70 rpm、拋光頭轉速70-90 rpm、抛光液流速200-300 1111/111丨11、拋光時間1-2 1^11;(2)然後在下壓力1.51^、拋 光盤的轉速25 rpm、拋光頭轉速25 rpm、分別使用傳統清 洗液和該發明清洗液，清洗液流速在300 ml/min，拋光時 間0.5-1 min ; (3)用清洗液及聚乙烯醇(pVA)滚刷對晶片表 面進行刷洗2 min，滚刷轉速為300 Γρ，清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4)再用去離子水及PVA滚 刷刷洗2 min，滾刷轉速為300 rpm清洗頭轉速28〇 rpm， 去離子水流量300 ml/min。清洗結果見圖一 a，一 B。 結果顯示，圖中亮線部分為金屬，使用傳統清洗液的 晶片（如圖一 A)’金屬表面有較嚴重的殘留；使用本發明 的清洗液清洗後的金屬表面（如圖一 B)光滑，未見明顯殘 留或腐蝕，缺陷率明顯下降，金屬表面的粗糙度得到明顯 改善。 實施例2 將含有0.5%多氨基多醚基四亞甲基膦酸和水為餘量 的清洗液(pH=2.5)用於化學機械拋光液拋光後的銅/二氧化 矽表面。（1)化學機械拋光液拋光銅金屬的程序為：下壓力 1.0-2.0 psi、拋光盤的轉速50-70 rpm、拋光頭轉速70-90 rpm、拋光液流速200-300 ml/min、搬光時間卜2 min ; (2) 然後在下壓力1.5 psi、拋光盤的轉速25 rpm、拋光頭轉速 9 1334169 9 i 25 rpm、分別使用傳統清洗液和該發明清洗液，清洗液流 速在300 ml/min，拋光時間0.5-1 min ; (3)用清洗液及聚 乙烯醇(PVA)滾刷對晶片表面進行刷洗2 min，滚刷轉速為 300 rpm ’清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4)再用去離子水及PVA滾刷刷洗2 min，滾刷轉 速為300 rpm清洗頭轉速280 rpm，去離子水流量300 ml/min。清洗結果見圖二A，二B。 結果顯不’使用傳統清洗液的晶片（如圖二A)，金屬 表面有較嚴重的腐蝕；使用本發明的清洗液清洗後的金屬 ‘· 表面（如圖二B)的光滑，未見明顯殘留或腐蝕，缺陷率明 顯下降，金屬表面的粗綠度得到明顯改善。 實施例3 將含有0.2%甲基續酸，聚丙稀酸（分子量5〇〇〇) 5000ppm和水為餘量的清洗液(ρΗ=2·5)用於化學機械拋光 液拋光後的銅/二氧化矽表面。（1)化學機械拋光液拋光銅 金屬的程序為：下壓力1.0-2.0 psi、拋光盤的轉速50-70 rpm、拋光頭轉迷70_9〇 rpin、拋光液流速200-300 _ ml/mm、拋光時間1-2 min ; (2)然後在下壓力i 5 psi、拋 光盤的轉速25 fpm、拋光頭轉速25 rpm、分別使用傳統清 洗液和該發明清洗液，清洗液流速在3〇〇 ml/min，拋光時 間0.5-1 min，（3)用清洗液及聚乙烯醇(pVA)滾刷對晶片表 面進行刷洗2 min，滾刷轉速為3〇〇 rpm，清洗頭轉速28〇 rpm ’清洗液流量300 ml/min ; (4)再用去離子水及pvA滾 刷刷洗2 min，滾刷轉速為3〇〇 rpm清洗頭轉速28〇 rpm， 去離子水流量300 ml/min® 實施例4 將含有1%檸檬酸和水為餘量的清洗液(pH=25)用於 1334169 i » 化學機械拋光液拋光後的銅/二氧化石夕表面。（1)化學機械 拋光液拋光銅金屬的程序為··下壓力10-2.0 psi、拋光盤 的轉速50-70 rpm、拋光頭轉速70·90 rpm、拋光液流速 200-300 ml/min、拋光時間卜2 min; (2)然後在下壓力1 5 psi、拋光盤的轉速25 rpm、拋光頭轉速25 rpm、分別使 用傳統清洗液和該發明清洗液’清洗液流速在300 ml/min，拋光時間0.5-1 min ; (3)用清洗液及聚乙烯醇 (PVA)滾刷對晶片表面進行刷洗2 min ’滾刷轉速為300 rp，清洗頭轉速280 rpm，清洗液流量300 mi/min ; (4)再 用去離子水及PVA滾刷刷洗2 min ’滾刷轉速為3〇〇 rpm ‘· 清洗頭轉速280 rpm，去離子水流量3〇〇 ml/min。 * 實施例5 將含有0.1%甘氨酸（Glycine)和聚丙烯酸（分子量 5000)100ppm和水為餘量的清洗液(pH=2.5)用於化學機械 拋光液拋光後的鋁/二氧化矽表面^ (1)化學機械拋光液拋 光銅金屬的程序為：下壓力1.0-2.0 psi、拋光盤的轉速50-70 rpm、拋光頭轉速70-90 rpm、拋光液流速200-300 ml/min、拋光時間1-2 min ; (2)然後在下壓力1.5 psi、拋 光盤的轉速25 rpm、拋光頭轉速25 rpm、分別使用傳統清 洗液和該發明清洗液，清洗液流速在300 ml/min，拋光時 間0.5-1 min ; (3)用清洗液及聚乙烯醇(PVA)滚刷對晶片表 面進行刷洗2 min，滾刷轉速為300 rp，清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4)再用去離子水及PVA滾 刷刷洗2 min ’滾刷轉速為300 rpm清洗頭轉速280 rpm， 去離子水流量300 ml/min。 實施例6 將含有0.1%丁烷膦醯基-1，2，4-三羧酸和水為餘量 1334169 的清洗液(pH=2.1)用於化學機械拋光液拋光後的銅/二氧化 矽表面。（1)化學機械拋光液拋光銅金屬的程序為：下壓力 1·〇-2.〇 pSi、拋光盤的轉速50-70 rpm、拋光頭轉速70-90 ΓΡ°ι、拋光液流速 200-300 ml/min、拋光時間 1-2 min ; (2) 然後在下壓力1.5 psi、拋光盤的轉速25 rpm、拋光頭轉速 25 rpm、分別使用傳統清洗液和該發明清洗液，清洗液流 速在300 ml/min，拋光時間0.5-1 min ; (3)用清洗液及聚 乙烯醇(PVA)滚刷對晶片表面進行刷洗2 min，滾刷轉速為 3〇〇 rp，清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4) 再用去離子水及PVA滾刷刷洗2 min，滾刷轉速為300 rPm清洗頭轉速280 rpm，去離子水流量300 ml/min。 實施例7 將含有0.2%環己基-二胺-4,亞曱基膦酸和水為餘量 的清洗液(pH=2.1)用於化學機械拋光液拋光後的鈕/氮化钽 /二氧化矽表面。（1)化學機械拋光液拋光銅金屬的程序 為：下壓力1.0-2.0 psi、拋光盤的轉速50-70 rpm、拋光頭 轉速70-90 rpm、拋光液流速200·300 ml/min、拋光時間 1-2 min ; (2)然後在下壓力1.5 psi、拋光盤的轉速25 rpm、拋光頭轉速25 rpm、分別使用傳統清洗液和該發明 清洗液，清洗液流速在300 ml/min，拋光時間0.5-1 min ; (3)用清洗液及聚乙烯醇(PVA)滚刷對晶片表面進行刷洗2 min ’滾刷轉速為300 rp，清洗頭轉速280 rpm，清洗液流 量300 ml/min ; (4)再用去離子水及PVA滚刷刷洗2 min， 滾刷轉速為300 rpm清洗頭轉速280 rpm，去離子水流量 300 ml/min。 實施例8 將含有0.02%環己基-二胺-4,亞曱基膦酸和0.5%擰 12 1334169 檬酸’水為餘量的清洗液(pH=3.0)用於化學機械拋光液拋 光後的鈦/二氧化矽表面。（1)化學機械拋光液拋光銅金屬 的程序為：下壓力1.0-2.〇 psi、拋光盤的轉速50_70 rpm、 拋光頭轉速70-90 rpm、拋光液流速πο-πο ml/min、拋光 時間卜2 min ; (2)然後在下壓力1.5 psi、拋光盤的轉速25 rpm、抛光頭轉速25 rpm、分別使用傳統清洗液和該發明 清洗液’清洗液流速在3〇〇 ml/min，拋光時間〇 5_丨min ; (3)用清洗液及聚乙烯醇(PVA)滚刷對晶片表面進行刷洗2 min ’滚刷轉速為300 rp ’清洗頭轉速280 rpm，清洗液流 量300 ml/min ; (4)再用去離子水及pVA滚刷刷洗2 min， 滾刷轉速為300 rpm清洗頭轉速280 rpm，去離子水流量 300 ml/min。 實施例9 將含有0.05% 丁烷膦醯基-1，2，4-三羧酸和0.8% 檸檬酸和水為餘量的清洗液(PH=3.5)用於化學機械拋光液 拋光後的銅/二氧化碎表面。（1)化學機械拋光液拋光銅金 屬的程序為：下壓力1.0-2.0 psi、拋光盤的轉速50-70 rpm、拋光頭轉速70-90 rpm、拋光液流速200-300 ml/min、拋光時間1-2 min; (2)然後在下壓力1.5 psi、拋 光盤的轉速25 rpm、拋光頭轉速25 rpm、分別使用傳統清 洗液和該發明清洗液，清洗液流速在300 ml/min，拋光時 間0.5-1 min; (3)用清洗液及聚乙稀醇(PVA)滾刷對晶片表 面進行刷洗2 min，滚刷轉速為300 Γρ，清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4)再用去離子水及PVA滾 刷刷洗2 min，滚刷轉速為300 rpm清洗頭轉速280 rpm ’ 去離子水流量300 ml/min。 實施例10 13 1334169 » · '· 將含有0.5% 丁烷膦醯基-1，2，4-三羧酸和2-丙烯 酿胺基-2 -甲基丙確酸1 〇ppm和水為餘量的清洗液 (pH=3.5)用於化學機械拋光液拋光後的銅/二氧化矽表面。 (1)化學機械拋光液拋光銅金屬的程序為：下壓力1.〇·2.〇 psi、拋光盤的轉速50-70 rpm、拋光頭轉速70-90 ipm、拋 光液流速200-300 ml/min、拋光時間卜2 min ; (2)然後在 下壓力1.5 psi、拋光盤的轉速25 rpm、拋光頭轉速25 rpm、分別使用傳統清洗液和該發明清洗液，清洗液流速 在300 ml/min，拋光時間0.5-1 min; (3)用清洗液及聚乙 φ 烯醇(pVA)滾刷對晶片表面進行刷洗2 min，滚刷轉速為 300 rp，清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4) 再用去離子水及PVA滚刷刷洗2 min，滚刷轉速為300 rpm清洗頭轉速28〇 rpm，去離子半流量300 ml/min。 本發明所使用的原料和試劑均為市售產品。 實施例11 將含有1%苯基膦酸和0.05%酒石酸和水為餘量的清 洗液(ρΗ=3.0)用於化學機械拋光液拋光後的鈦/二氧化矽表 面。（1)化學機械拋光液拋光銅金屬的程序為：下壓力1.0-2.0 psi、拋光盤的轉速50-70 rpm、拋光頭轉速70-90 rpm、拋光液流速200-300 ml/min、拋光時間卜2 min ; (2) 然後在下壓力1.5 psi、拋光盤的轉速25 rpm、拋光頭轉速 25 rpm、分別使用傳統清洗液和該發明清洗液，清洗液流 速在300 ml/min，拋光時間0.5-1 min ; (3)用清洗液及聚 乙烯醇(PVA)滚刷對晶片表面進行刷洗2 min，滚刷轉速為 300 Γρ，清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4) 再用去離子水及PVA滾刷刷洗2 min ’滾刷轉速為300 rPm清洗頭轉速280 rpm ’去離子水流量300 ml/min。 1334169 實施例12 將含有1%二曱基磺酸和5%琥珀酸和水為餘量的清 洗液(pH=3.0)用於化學機械拋光液拋光後的鈦表面。（1)化 學機械拋光液拋光銅金屬的程序為：下壓力1.〇-2.0 psi、 抛光盤的轉速50-70 rpm、拋光頭轉速70-90 rpm、抛光液 流速200-300 ml/min、拋光時間卜2 min ; (2)然後在下壓 力1.5 psi、拋光盤的轉速25 rpm、拋光頭轉速25 rpm、分 別使用傳統清洗液和該發明清洗液，清洗液流速在300 ml/min，拋光時間0.5-1 min ; (3)用清洗液及聚乙烯醇 (PVA)滾刷對晶片表面進行刷洗2 min，滾刷轉速為300 rp，清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4)再 用去離子水及PVA滚刷刷洗2 min，滾刷轉速為300 rpm 清洗頭轉速280 rpm，去離子水流量300 ml/min。 實施例13 將含有1%丁基磺酸内酯和0.05%甲硫氨酸和水為餘 量的清洗液(pH=3.0)用於化學機械拋光液拋光後的鈦/二氧 化矽表面。（1)化學機械拋光液拋光銅金屬的程序為：下壓 力1.0-2.0 psi、拋光盤的轉速50-70 rpm、拋光頭轉速70-90 rpm、拋光液流速200-300 ml/min、抛光時間1-2 min ; (2)然後在下壓力1.5 psi、拋光盤的轉速25 rpm、拋光頭 轉速25 rpm、分別使用傳統清洗液和該發明清洗液，清洗 液流速在300 ml/min，拋光時間0.5-1 min ; (3)用清洗液 及聚乙烯醇(PVA)滾刷對晶片表面進行刷洗2 min，滾刷轉 速為300 Γρ，清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4)再用去離子水及PVA滚刷刷洗2 min，滾刷轉 速為300 rpm清洗頭轉速280 rpm’去離子水流量300 ml/min 〇 15 1334169The μίίί lotion also contains a pH adjuster, a surfactant and/or a polymeric metal antiseptic. The polymer metal anticorrosive inhibitor is a polypropylene compound, a acrylic acid compound and a styrene copolymer compound, a copolymer compound of a propylene compound and a cis-acid needle, a copolymer compound of an acrylic compound and a propylene compound, and a lining. A ruthenium acid complex, a propylene contact = a total of (four) or a acrylic acid acrylic acid - squaric acid - acid salt tetrapolymer. The polymer metal antiseptic inhibitor has a molecular weight in the range of 2,0 〇〇 3 , 〇〇〇 〇〇〇. The polycarboxylic acid and/or its salt is a compound of the formula: ψ Ri γ I | π 〇" c — an alkyl group of CO〇R3”η less than 3, R3 wherein the core and RZ are hydrogen atoms or carbon by themselves. The number of atoms is H, K, Na or NH4. The polyacrylic compound is preferably a polyacrylic acid. 1334169 30,000 The polyacrylic acid compound preferably has a molecular weight range of 5, and the polyacrylic acid compound has a weight percentage of 5 ppm by weight. Read the good ground for 10PPm~ This hair_cleansing (four) contains the money and the mixture of the silk and three wow "than the 嗤 and / or imi wow. The cleaning solution also contains nitrogen-containing heterocyclic compounds in a percentage by weight 〇 ~ 〇 · 1 % 〇® The pH of the cleaning liquid of the present invention is preferably in the range of 2 to 7. In addition, the carrier is an alcohol and/or water. The cleaning liquid of the present invention can be applied to the cleaning of a metal substrate. The metal substrate is copper, aluminum, group, nitrided group, titanium, titanium nitride, silver or gold. In the present invention, the β lotion can be used in the following procedures: polishing, etching (after strong photoresist) , deposition and other protection steps. Because the chemical additive is used in the cleaning liquid of the invention, the interference on the subsequent process is reduced, the surface pitting of the metal material is greatly reduced, the degree of surface corrosion is reduced, and the defect is reduced, thereby The cleaning efficiency and the product yield increase the profit rate. The positive progress of the invention is that the cleaning liquid of the invention can greatly reduce the corrosion degree of the metal material, thereby (1) significantly reducing the defects; and greatly improving the surface of the metal. Flatness (3) Improve product yield (4) Improve process operation window. The advantages and spirit of the present invention can be further understood by the following detailed description of the invention. [Embodiment] In order to achieve the above-mentioned scope of the present invention, The technical means used and the remaining effects of 8 1334169 I are described as follows: Example 1 will contain 2% citric acid (Citric acid) and polyacrylic acid (molecular weight 5000) lOppm and ^ The cleaning solution (pH=2 4) for the chemical polishing liquid is polished to the surface of the chemical polishing liquid. The procedure for polishing the copper metal by the chemical mechanical polishing liquid is: the lower pressure l.〇-2.〇psi , the rotation speed of the polishing disc is 50-70 rpm, the polishing head speed is 70-90 rpm, the polishing liquid flow rate is 200-300 1111/111丨11, the polishing time is 1-2 1^11; (2) and then the lower pressure is 1.51^, the polishing disc The rotation speed is 25 rpm, the polishing head speed is 25 rpm, the conventional cleaning liquid and the cleaning liquid of the invention are respectively used, the cleaning liquid flow rate is 300 ml/min, the polishing time is 0.5-1 min; (3) the cleaning liquid and the polyvinyl alcohol (pVA) are used. The roller brush scrubs the surface of the wafer for 2 min, and the rolling speed is 300 Γρ, the cleaning head The rotation speed is 280 rpm, the flow rate of the cleaning liquid is 300 ml/min; (4) It is brushed with deionized water and PVA roller brush for 2 min, the rotation speed of the brush is 300 rpm, the head speed is 28 rpm, and the deionized water flow is 300 ml/min. The cleaning results are shown in Figure 1a, Figure A. The results show that the bright line in the figure is metal, and the wafer using the conventional cleaning solution (Fig. 1A) has a more serious residue on the metal surface; after cleaning with the cleaning solution of the invention The metal surface (Fig. 1B) is smooth, no obvious residue or corrosion, the defect rate is significantly reduced, and the roughness of the metal surface is significantly improved. Example 2 A cleaning solution (pH = 2.5) containing 0.5% polyaminopolyether tetramethylenephosphonic acid and water was used for the surface of the copper/cerium oxide after chemical mechanical polishing. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2.0 psi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70-90 rpm, polishing liquid flow rate 200-300 ml/min, moving light Time 2 min; (2) Then at a lower pressure of 1.5 psi, a polishing disc speed of 25 rpm, a polishing head speed of 9 1334169 9 i 25 rpm, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning fluid flow rate is 300 ml/min Polishing time 0.5-1 min; (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min, the brush speed is 300 rpm 'washing head speed 280 rpm, cleaning liquid flow 300 ml/ (4) Brush again with deionized water and PVA roller brush for 2 min, the brush speed is 300 rpm, the head speed is 280 rpm, and the deionized water flow is 300 ml/min. The cleaning results are shown in Figures 2A and 2B. The result is not 'the wafer using the conventional cleaning solution (as shown in Figure 2A), the metal surface has more serious corrosion; the smoothness of the metal '· surface (Fig. 2B) after cleaning with the cleaning solution of the invention is not obvious Residual or corrosive, the defect rate is significantly reduced, and the coarse greenness of the metal surface is significantly improved. Example 3 A cleaning solution containing 0.2% methyl post-acid, polyacrylic acid (molecular weight 5 〇〇〇) 5000 ppm and water as a balance (ρΗ=2.5) was used for chemical mechanical polishing liquid polishing of copper/two Oxide surface. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2.0 psi, polishing plate rotation speed 50-70 rpm, polishing head turning 70_9〇rpin, polishing liquid flow rate 200-300 _ ml/mm, polishing Time 1-2 min; (2) Then at a lower pressure i 5 psi, a polishing disk speed of 25 fpm, a polishing head rotation speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning liquid flow rate is 3 〇〇 ml / min Polishing time 0.5-1 min, (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (pVA) roller brush for 2 min, the rolling speed is 3 rpm, and the cleaning head speed is 28 rpm 'cleaning liquid flow 300 ml/min; (4) Brush again with deionized water and pvA roller brush for 2 min, the brush speed is 3 rpm, the head speed is 28 rpm, and the deionized water flow rate is 300 ml/min®. Example 4 will contain 1% citric acid and water are the balance of the cleaning solution (pH=25) for the 1334169 i » chemical mechanical polishing solution after polishing the copper/earic dioxide surface. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: down-pressure 10-2.0 psi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70.90 rpm, polishing liquid flow rate 200-300 ml/min, polishing Time 2 min; (2) then at a lower pressure of 15 psi, a polishing disc speed of 25 rpm, a polishing head speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution respectively, the cleaning fluid flow rate is 300 ml/min, polishing time 0.5-1 min; (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min 'Rolling speed is 300 rp, cleaning head speed is 280 rpm, cleaning liquid flow is 300 mi/min; 4) Brush again with deionized water and PVA roller brush for 2 min 'Rolling speed of 3 rpm '· Wash head speed 280 rpm, deionized water flow 3 〇〇 ml / min. * Example 5 A cleaning solution (pH = 2.5) containing 0.1% glycine (Glycine) and polyacrylic acid (molecular weight 5000) and water as a balance for the surface of aluminum/cerium oxide polished by chemical mechanical polishing liquid ^ ( 1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2.0 psi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70-90 rpm, polishing liquid flow rate 200-300 ml/min, polishing time 1 -2 min ; (2) Then at a lower pressure of 1.5 psi, a polishing disc speed of 25 rpm, a polishing head rotation speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning liquid flow rate is 300 ml/min, and the polishing time is 0.5- 1 min; (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min, the brush speed is 300 rp, the cleaning head speed is 280 rpm, and the cleaning liquid flow rate is 300 ml/min; (4) Then brush with deionized water and PVA roller for 2 min. 'Rolling speed is 300 rpm. The head speed is 280 rpm and the deionized water flow is 300 ml/min. Example 6 A cleaning solution (pH=2.1) containing 0.1% butanephosphine-decyl-1,2,4-tricarboxylic acid and water as the balance 1334169 was used for copper/cerium oxide after chemical mechanical polishing surface. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1·〇-2.〇pSi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70-90 ΓΡ°ι, polishing liquid flow rate 200-300 Ml/min, polishing time 1-2 min; (2) Then at a lower pressure of 1.5 psi, a polishing plate speed of 25 rpm, a polishing head rotation speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning liquid flow rate is 300 ml /min, polishing time 0.5-1 min; (3) brushing the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min, the rolling speed is 3 〇〇rp, the cleaning head speed is 280 rpm, the cleaning solution Flow rate 300 ml/min; (4) Brush with deionized water and PVA roller for 2 min. The brush speed is 300 rPm, the head speed is 280 rpm, and the deionized water flow is 300 ml/min. Example 7 A cleaning solution (pH=2.1) containing 0.2% cyclohexyl-diamine-4, fluorenylphosphonic acid and water as a balance for the button/tantalum nitride/dioxide after chemical mechanical polishing矽 surface. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2.0 psi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70-90 rpm, polishing liquid flow rate 200·300 ml/min, polishing time 1-2 min; (2) Then at a lower pressure of 1.5 psi, a polishing plate speed of 25 rpm, a polishing head rotation speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning liquid flow rate is 300 ml/min, and the polishing time is 0.5. -1 min ; (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min 'Rolling speed is 300 rp, cleaning head speed is 280 rpm, cleaning liquid flow is 300 ml/min; (4 Then brush with deionized water and PVA roller for 2 min, the brush speed is 300 rpm, the head speed is 280 rpm, and the deionized water flow is 300 ml/min. Example 8 A cleaning solution (pH=3.0) containing 0.02% cyclohexyl-diamine-4, fluorenylphosphonic acid and 0.5% of 12 1334169 citric acid' water was used for polishing after chemical mechanical polishing Titanium/cerium oxide surface. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2. 〇psi, polishing plate rotation speed 50_70 rpm, polishing head rotation speed 70-90 rpm, polishing liquid flow rate πο-πο ml/min, polishing time 2 min; (2) then at a lower pressure of 1.5 psi, a polishing disk speed of 25 rpm, a polishing head speed of 25 rpm, respectively using a conventional cleaning solution and the inventive cleaning solution 'cleaning fluid flow rate at 3 〇〇 ml / min, polishing time 〇5_丨min; (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min 'Rolling speed of 300 rp ' cleaning head speed 280 rpm, cleaning liquid flow 300 ml / min; (4) Brush again with deionized water and pVA roller brush for 2 min, the brush speed is 300 rpm, the head speed is 280 rpm, and the deionized water flow is 300 ml/min. Example 9 A cleaning solution (pH=3.5) containing 0.05% butanephosphine-decyl-1,2,4-tricarboxylic acid and 0.8% citric acid and water as a balance for copper after chemical mechanical polishing / Dioxide ash surface. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2.0 psi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70-90 rpm, polishing liquid flow rate 200-300 ml/min, polishing time 1-2 min; (2) Then at a lower pressure of 1.5 psi, a polishing plate speed of 25 rpm, a polishing head speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning liquid flow rate is 300 ml / min, polishing time 0.5 -1 min; (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min, the brush speed is 300 Γρ, the cleaning head speed is 280 rpm, and the cleaning liquid flow rate is 300 ml/min; 4) Brush again with deionized water and PVA roller brush for 2 min. The brush speed is 300 rpm. The head speed is 280 rpm' Deionized water flow rate is 300 ml/min. Example 10 13 1334169 » · '· will contain 0.5% butane phosphine fluorenyl-1,2,4-tricarboxylic acid and 2-propenyl amido-2-methylpropionic acid 1 〇 ppm and water A quantity of cleaning solution (pH = 3.5) was used for the copper/cerium oxide surface after chemical mechanical polishing. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1. 〇·2.〇psi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70-90 ipm, polishing liquid flow rate 200-300 ml/ Min, polishing time 2 min; (2) then at a lower pressure of 1.5 psi, a polishing plate speed of 25 rpm, a polishing head rotation speed of 25 rpm, respectively using a conventional cleaning solution and the inventive cleaning solution, the cleaning liquid flow rate is 300 ml / min, Polishing time 0.5-1 min; (3) Brush the surface of the wafer with a cleaning solution and a polyethylene acetyl enol (pVA) brush for 2 min, the brush speed is 300 rp, the cleaning head speed is 280 rpm, and the cleaning liquid flow is 300 ml. /min; (4) Brush with deionized water and PVA roller for 2 min, the brush speed is 300 rpm, the head speed is 28 rpm, and the deionization half flow is 300 ml/min. The raw materials and reagents used in the present invention are all commercially available products. Example 11 A cleaning solution (ρ Η = 3.0) containing 1% phenylphosphonic acid and 0.05% tartaric acid and water was used for the surface of the titanium/cerium oxide after chemical mechanical polishing. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2.0 psi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70-90 rpm, polishing liquid flow rate 200-300 ml/min, polishing time 2 min; (2) Then at a lower pressure of 1.5 psi, a polishing disc speed of 25 rpm, a polishing head rotation speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning fluid flow rate is 300 ml/min, and the polishing time is 0.5- 1 min; (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min, the brush speed is 300 Γρ, the cleaning head speed is 280 rpm, and the cleaning liquid flow rate is 300 ml/min; (4) Then brush with deionized water and PVA roller for 2 min 'Rolling speed of 300 rPm cleaning head speed 280 rpm' deionized water flow 300 ml/min. 1334169 Example 12 A cleaning solution (pH = 3.0) containing 1% dimercaptosulfonic acid and 5% succinic acid and water was used for the surface of the titanium after chemical mechanical polishing. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1. 〇-2.0 psi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70-90 rpm, polishing liquid flow rate 200-300 ml/min, Polishing time 2 min; (2) Then at a lower pressure of 1.5 psi, a polishing disc speed of 25 rpm, a polishing head rotation speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning liquid flow rate is 300 ml/min, polishing time 0.5-1 min; (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min, the brush speed is 300 rp, the cleaning head speed is 280 rpm, and the cleaning liquid flow rate is 300 ml/min; 4) Brush again with deionized water and PVA roller brush for 2 min. The brush speed is 300 rpm. The head speed is 280 rpm and the deionized water flow is 300 ml/min. Example 13 A cleaning solution (pH = 3.0) containing 1% butyl sultone and 0.05% methionine and water was used for the surface of the titanium/niobium oxide after chemical mechanical polishing. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2.0 psi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70-90 rpm, polishing liquid flow rate 200-300 ml/min, polishing time 1-2 min; (2) Then at a lower pressure of 1.5 psi, a polishing plate speed of 25 rpm, a polishing head rotation speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning liquid flow rate is 300 ml/min, and the polishing time is 0.5. -1 min; (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min, the brush speed is 300 Γρ, the cleaning head speed is 280 rpm, and the cleaning liquid flow rate is 300 ml/min; ) Brush with deionized water and PVA roller brush for 2 min, brush speed is 300 rpm, head speed 280 rpm' deionized water flow 300 ml/min 〇 15 1334169
v ' I - 實施例14 將含有5%羥脯氨酸和聚丙烯酸5000ppm(分子量為 20 ’ 000)和水為餘量的清洗液(pH=7.0)用於化學機械拋光 液拋光後的鈦/二氧化矽表面。（1)化學機械拋光液拋光銅 金屬的程序為：下壓力1.0-2.〇 pSi、拋光盤的轉速50-70 rpm、拋光頭轉速7〇_9〇 Γριη、拋光液流速200-300 ml/min、拋光時間丨_2 min ; (2)然後在下壓力1.5 psi、拋 光盤的轉速25rpm、拋光頭轉速25rpin、分別使用傳統清 洗液和該發明清洗液，清洗液流速在300 ml/min，拋光時 •攀 間Ο.5·1 ; (3)用清洗液及聚乙烯醇(PVA)滚刷對晶片表 面進行刷洗2 min，滾刷轉速為300 rp，清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4)再用去離子水及PVA滚 刷刷洗2 min ’滾刷轉速為3〇〇 rpm清洗頭轉速280 rpm， 去離子水流量3 00 ml/min。 實施例15 將含有1%天門冬氨酸和聚丙稀酸1 Oppm(分子量為 10 ’ 000)和水為餘量的清洗液(pH=7.0)用於化學機械拋光 鲁 液拋光後的鈦/二氧化石夕表面。（1)化學機械拋光液拋光銅 金屬的程序為：下壓力1.0-2.0 pSi、拋光盤的轉速50-70 rpm、拋光頭轉速70-90 rpm、拋光液流速200-300 ml/min、拋光時間1-2 min ; (2)然後在下壓力1.5 psi、拋 光盤的轉速25 rpm、拋光頭轉速25 rpm、分別使用傳統清 洗液和該發明清洗液’清洗液流速在3〇〇 mi/mm，拋光時 間0.5-1 min ; (3)用清洗液及聚乙烯醇(PVA)滚刷對晶片表 面進行刷洗2 min ’滾刷轉速為300 rp，清洗頭轉速280 rpm，清洗液流量300 ml/min ;⑷再用去離子水及PVA滾 刷刷洗2 min，滾刷轉速為300 rpm清洗頭轉速280 i*pm， 去離子水流量3 00 ml/min。 16 1334169 螯 實施例16 將含有0.1%環己基·二胺-4,亞曱基膦酸和聚丙烯酸 500ppm(分子量為30，000)和水為餘量的清洗液(pH=7.0) 用於化學機械拋光液拋光後的钽/二氧化矽表面。（1)化學 機械拋光液拋光銅金屬的程序為：下壓力1.0-2.0 psi、拋 光盤的轉速50-70 rpm、拋光頭轉速70-90 i*pm、拋光液流 速200-300 ml/min、拋光時間1-2 min ; (2)然後在下壓力 1.5 psi、拋光盤的轉速25 rpm、拋光頭轉速25 rpm、分別 使用傳統清洗液和該發明清洗液，清洗液流速在300 ml/min ’拋光時間0.5-1 min ; (3)用清洗液及聚乙烯醇 (PVA)滚刷對晶片表面進行刷洗2 min，滾刷轉速為300 Φ ’清洗頭轉速280 rpm，清洗液流量300 ml/min ; (4)再 用去離子水及PVA滾刷刷洗2 min，滾刷轉速為300 rpm 清洗頭轉速280 rpm，去離子水流量300 ml/min。 本發明所使用的原料和試劑均為市售產品。 藉由以上較佳具體實施例之詳述，係希望能更加清楚 描述本發明之特徵與精神，而並非以上述所揭露的較佳具體實施 例來對本發明之範疇加以限制。相反地，其目的是希望能涵蓋各 種改變及具相等性的安排於本發明所欲申請之專利範圍的範嘴 内二因此，本發明所申請之專利範圍的範疇應該根據上述的說明 作最寬廣的解釋’以致使其涵蓋所有可能的改變以及具相等性 安排。 17 UJ4109 【圖式簡單說明】 · 洗後洗溶液(1%檸檬酸，αι%苯並三吐)清 夕表面的掃描電子顯微鏡(SEM)圖。 ㈣f 發明實施例1中的清洗溶液清洗後的銅/组/二氧 化矽表面崎描電子酿鏡(SEM)圖。 ίΛ^ι/^Τ* A為使用傳統清洗溶液(1%捧檬酸，G.1%苯並三唾)後 、銅鈕/二氧切表_掃描電子顯微鏡邮州圖。 圖二Β為本發明實施例2中清洗溶液清洗後的 矽表面的掃描電子顯魏(SEM)目。 ^ 一氧化 【主要元件符號說明】 無v ' I - Example 14 A cleaning solution (pH = 7.0) containing 5% hydroxyproline and polyacrylic acid 5000 ppm (molecular weight 20 ' 000) and water for the chemical mechanical polishing liquid polished titanium / Ceria surface. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2. 〇pSi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 7〇_9〇Γριη, polishing liquid flow rate 200-300 ml/ Min, polishing time 丨_2 min; (2) then at a lower pressure of 1.5 psi, a polishing disk speed of 25 rpm, a polishing head speed of 25 rpin, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning liquid flow rate is 300 ml / min, polishing (C) brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min, the brush speed is 300 rp, the cleaning head speed is 280 rpm, and the cleaning liquid flow rate is 300. Ml/min; (4) Brush with deionized water and PVA brush for 2 min. 'Rolling speed is 3 rpm. The head speed is 280 rpm, and the deionized water flow is 3 00 ml/min. Example 15 A cleaning solution (pH=7.0) containing 1% aspartic acid and polyacrylic acid 1 Oppm (molecular weight 10 '000) and water as a balance was used for chemical mechanical polishing of titanium liquid after polishing Oxidized stone eve surface. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2.0 pSi, polishing disc rotation speed 50-70 rpm, polishing head rotation speed 70-90 rpm, polishing liquid flow rate 200-300 ml/min, polishing time 1-2 min; (2) then at a lower pressure of 1.5 psi, a polishing disk speed of 25 rpm, a polishing head speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution respectively, the cleaning fluid flow rate is 3 〇〇mi/mm, polished Time 0.5-1 min; (3) Brush the surface of the wafer with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min 'Rolling speed is 300 rp, cleaning head speed is 280 rpm, cleaning liquid flow is 300 ml/min; (4) Brush again with deionized water and PVA roller brush for 2 min, the brush speed is 300 rpm, the head speed is 280 i*pm, and the deionized water flow is 3 00 ml/min. 16 1334169 Chelating Example 16 A cleaning solution (pH=7.0) containing 0.1% cyclohexyldiamine-4, fluorenylphosphonic acid and polyacrylic acid 500 ppm (molecular weight 30,000) and water for the remainder The surface of the bismuth/cerium oxide after mechanical polishing. (1) The procedure for polishing copper metal by chemical mechanical polishing liquid is: lower pressure 1.0-2.0 psi, polishing plate rotation speed 50-70 rpm, polishing head rotation speed 70-90 i*pm, polishing liquid flow rate 200-300 ml/min, Polishing time 1-2 min; (2) Then at a lower pressure of 1.5 psi, a polishing disc speed of 25 rpm, a polishing head speed of 25 rpm, using a conventional cleaning solution and the inventive cleaning solution, respectively, the cleaning fluid flow rate is 300 ml/min 'polishing Time 0.5-1 min; (3) The surface of the wafer was brushed with a cleaning solution and a polyvinyl alcohol (PVA) roller brush for 2 min, the rolling speed was 300 Φ 'the cleaning head speed was 280 rpm, and the cleaning liquid flow rate was 300 ml/min; (4) Brush again with deionized water and PVA roller brush for 2 min, the brush speed is 300 rpm, the head speed is 280 rpm, and the deionized water flow rate is 300 ml/min. The raw materials and reagents used in the present invention are all commercially available products. The features and spirit of the present invention are intended to be more apparent from the detailed description of the preferred embodiments. On the contrary, the intention is to cover various modifications and equivalent arrangements within the scope of the patent application of the invention. Therefore, the scope of the patent scope of the invention should be broadest according to the above description. The interpretation 'so that it covers all possible changes and equivalence arrangements. 17 UJ4109 [Simple description of the diagram] · Scanning electron microscope (SEM) image of the surface of the wash solution (1% citric acid, αι% benzotriazole). (4) f A copper/group/yttria surface-sawed electron-stained mirror (SEM) pattern after cleaning of the cleaning solution in Inventive Example 1. Λ Λ ^ι / ^ Τ * A is the use of traditional cleaning solution (1% citrate, G.1% benzotrisole), copper button / dioxometer _ scanning electron microscope postal map. Fig. 2 is a scanning electron show (SEM) of the surface of the crucible after cleaning of the cleaning solution in Example 2 of the present invention. ^ Oxidation [Main component symbol description] None
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