201042031 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種對附著氧化鈽之被洗淨物 除去該氧化鈽之洗淨液及使用該洗淨液之洗淨方 【先前技術】 以超大型積體電路（ULSI)的高性能化爲目 0 朝電路設計的細微化進展。爲了形成奈米等級爲 的非常細微的電路構造，需要許多至今沒有被應 製造技術之製造步驟。 特別是作爲半導體基板上形成細微構造之最 驟，係使用光學手段之曝光•微影步驟。爲了製 構造，在半導體基板的表面上集結相同均勻的焦 板表面的平坦性有不可分之關係。亦即，基板表 性不佳的情況下，基板表面上產生聚焦部分與不 〇 ，在不聚焦部分無法產生所期望的細微構造，生 低變大。而且，隨著細微化持續進展，關於平坦 容許範圍變小，更進一步地提高基板表面的平坦 〇 而且，除平坦化的要求，亦要求以提高生產 的之步驟時間的縮短。因此，除細微加工的加工 亦需要可使步驟高速化之技術。從所謂技術上的 爲確保平坦性的技術，一般進行化學機械硏磨（ 於CMP步驟，使用粒狀的硏磨粒，高速地進行 ，可洗淨 法。 的，持續 止細微化 用之新的 重要的步 作該細微 點，與基 面的平坦 聚焦部分 產性的降 性之可能 化之要求 效率爲目 精度外， 背景，作 CMP )。 半導體基 201042031 板表面的硏磨（平坦化）。 於前述c Μ P步驟’例如使用氧化矽糊漿之技術。但 是’因於該CMP步驟殘留成爲殘渣之氧化矽糊漿，進行 將其洗淨除去之步驟。作爲洗淨所使用的洗淨劑，例如以 除去粒子、有機雜質及金屬雜質爲目的之下述專利文獻1 記載之洗淨液。此外，例如以除去半導體基板上的粒子爲 目的之下述專利文獻2記載之半導體基板用洗淨液。 另一方面’於CMP步驟，亦進行使用氧化铈作爲硏 磨粒之化學機械硏磨。但是，前述洗淨劑有難以除去氧化 姉的殘渣之問題。結果，成爲半導體裝置的生產性降低之 主因。 先前技術文獻 專利文獻1 :特開2002-270566號公報 專利文獻2:特開2005-60660號公報 【發明內容】 [發明所欲解決之課題] 本發明係以提供對表面附著氧化鈽之被洗淨物，使氧 化鈽溶解成爲鈽離子而可洗淨除去之洗淨液及使用其之洗 淨方法爲目的。 [解決課題之手段] 本案之發明人等，爲了解決前述傳統的問題點，對於 洗淨液及使用其之洗淨方法加以檢討。結果，發現含有氟 -6- 201042031 化氫、與選自鹽酸、硝酸、硫酸、乙酸、磷酸、碘酸及溴 化氫酸所成群的至少1種酸、與水之洗淨液，可洗淨除去 氧化铈，因而完成本發明。 亦即，關於本發明之洗淨液，爲了解決前述課題，其 係除去氧化鈽之洗淨液，其特徵爲由含有氟化氫、與選自 鹽酸、硝酸、硫酸、乙酸、磷酸、碘酸及溴化氫酸所成群 的至少1種酸、與水所構成，使前述氧化鈽溶解成爲鈽離 0 子而除去。 氟化氫溶液，因其氧化力的強度，可使氧化铈溶解成 爲姉離子。但是，因溶解的铈離子再度以雜質再附著於被 洗淨物的表面，結果，除去氧化鈽仍有困難。另一方面， 於使用前述酸作爲洗淨液的情況，因爲此等酸之氧化力弱 ，難以使氧化鈽溶解成爲铈離子，且亦無法除去。 但是，如前述之構成，組合氟化氫與前述酸之洗淨液 ’氟化氫使氧化铈成爲鋪離子溶解於洗淨液中，同時前述 〇 酸使其不再附著於被洗淨物的表面而可除去。亦即，若是 前述構成的洗淨液，可洗淨除去傳統洗淨液不易除去之氧 化铈。藉此，例如使用氧化鈽作爲硏磨粒之半導體基板的 化學機械硏磨步驟後的洗淨，只要使用本發明的洗淨液， 可有效地洗淨除去氧化鈽，可期望提高半導體裝置的生產 效率。 於前述構成，前述氟化氫的濃度在0.00 1〜20重量％ 的範圍內，前述酸的濃度在0·001〜50重量％的範圍內較 理想。藉由前述氟化氫的濃度爲0.001重量％以上，可防 201042031 止對氧化铈之溶解性能之降低，同時藉由2 0重量％以下， 可防止被洗淨物被蝕刻。而且’藉由前述列舉之酸的濃度 爲0.0 0 1重量％以上，可確保從被洗淨物除去氧化鈽之性 能，同時藉由5 0重量％以下，可防止對氧化鈽之溶解性能 之降低。 而且，關於本發明的洗淨方法，爲了解決前述課題’ 其係使用前述記載的洗淨液之洗淨法，其特徵爲藉由使附 著氧化铈之被洗淨物與前述洗淨液接觸，使氧化铈溶解成 爲铈離子而除去。 本發明的洗淨液藉由與附著氧化铈之被洗淨物接觸， 氧化鈽成爲鈽離子溶解於洗淨液中，同時可使其不再附著 於被洗淨物的表面而除去。藉此，例如於半導體裝置的製 造製程，即使採用使用氧化铈作爲硏磨粒之半導體基板的 化學機械硏磨步驟，可從半導體基板表面洗淨除去氧化鈽 的殘渣，可提高半導體裝置的生產性。 於前述方法，前述洗淨液的蝕刻速率，其液溫25 °C之 情況下對被洗淨物之蝕刻速率爲1 ο A/分以下較理想。藉由 本發明的洗淨方法所使用的洗淨液對被洗淨物之蝕刻速率 抑制爲1 0A/分以下，可防止對被洗淨物本身之蝕刻。結果 ’可抑制被洗淨物的表面粗糙度之增加，可洗淨除去氧化 鈽。 而且’於前述方法，前述洗淨液的洗淨時之液溫爲30 °C以下較理想。 而且’於前述方法，前述被洗淨物係以氧化铈糊漿進 -8- 201042031 行化學機械硏磨者較理想。 [發明的效果] 本發明藉由前述說明的手段，可發揮以下所述之效果 0 亦即’根據本發明，可有效地進行傳統的酸洗淨液有 困難之氧化鈽的洗淨除去。結果，例如於半導體裝置的製 0 造製程’即使採用使用氧化铈作爲硏磨粒之半導體基板的 化學機械硏磨（CMP )步驟，可從半導體基板表面洗淨除 去氧化鋪的殘渣，可提高半導體裝置的生產性。 【實施方式】 以下說明關於本發明的洗淨液。 關於本發明的洗淨液，其係由含有氟化氫、與選自鹽 酸、硝酸、硫酸、乙酸、磷酸、碘酸及溴化氫酸所成群的 Q 至少1種酸、與水所構成。而且，關於本發明的洗淨液， 以前述列舉的酸爲主成分之構成較理想。此處，例如過氧 化氫與前述酸的組合所成的洗淨液時，因該洗淨液難以使 氧化铈溶解成爲鈽離子，無法洗淨除去氧化鈽。本發明係 藉由使洗淨液中含有氟化氫，藉由其氧化力使氧化姉溶解 成爲鈽離子。而且，由前述酸單獨所成的洗淨液，因本身 難以使氧化鈽溶解，從被洗淨物洗淨除去更加困難。但是 ，藉由倂用此等酸與氟化氫，不只是使氧化鈽離子溶解於 洗淨液中，亦可從被洗淨物表面除去。亦即，本發明的洗 -9- 201042031 淨液，藉由氟化氫與前述酸的組合，可洗淨除去氧化鈽。 此外，铈離子係指Ce3+、Ce4+、此等的水合物或此等的錯 離子。 前述氟化氫對洗淨液全部之濃度在0.001〜20重量％ 的範圍內較理想，0.0 0 1〜5重量％的範圍內更理想。氟化 氫的濃度未達0.001重量％時，使氧化铈溶解成爲铈離子 之溶解性能降低，結果，氧化铈的洗淨效果降低，所以不 理想。另一方面，氟化氫的濃度超過20重量％時，被洗淨 物則被蝕刻，其表面粗糙度有增加的情形。而且，洗淨處 理後，使成爲排水之洗淨液中的氟化氫無害化時，所需費 用及時間有增加的情形。 前述列舉的酸中，於本發明，以鹽酸、硝酸、硫酸或 磷酸較理想。若是此等酸，溶解铈離子的洗淨液，不殘留 於被洗淨物表面而容易除去。 選自鹽酸、硝酸、硫酸、乙酸、磷酸、碘酸及溴化氫 酸所成群的至少1種酸對洗淨液全部之濃度在0.001〜50 重量％的範圍內較理想，0.001〜20重量％的範圍內更理想 。前述酸的濃度未達0.001重量％時，從被洗淨物除去氧 化鈽之除去性能有降低的情形。另一方面，超過50重量％ 時，洗淨處理後，使成爲排水之洗淨液中的酸無害化時， 所需費用及時間有增加的情形。再者，蒸發揮發性的成分 ，洗淨液的組成產生變動，安定的洗淨處理有變困難的情 形。 於本發明的洗淨液，亦可添加界面活性劑。藉此，降 -10- 201042031 低洗淨液的表面張力，提高對被洗淨物表面的潤濕性。結 果，對被洗淨物可均勻地發揮在更廣範圍下洗淨除去效果 ，可期望提高生產性。前述界面活性劑無特別限制，例如 脂肪族羧酸、其鹽等的陰離子系界面活性劑等。而且，亦 可使用聚乙烯醇烷醚等非離子系界面活性劑、脂肪族胺、 或其鹽等的陽離子系界面活性劑。 前述界面活性劑的添加量適合在0.001〜0.1重量％的 0 範圍內，0_003〜0.05重量％的範圍內較理想。藉由添加界 面活性劑，可抑制經洗淨處理之被洗淨物的表面之皴裂。 再者，改善對被洗淨物之潤濕性，可期望面內洗淨效果的 均勻性。但是，前述添加量未達〇. 〇 〇 1重量％時，因洗淨 液的表面張力沒有充分降低，有潤濕性的提高效果不足的 情形。而且，前述添加量超過0.1重量％時，不僅無法得 到平衡其的效果，消泡性惡化，被洗淨物表面附著氣泡， 有產生洗淨不均勻的情形。 〇 洗淨液的pH爲2以下較理想，1以下更理想。藉由 pH爲2以下，可安定铈離子的溶解狀態，可提高洗淨效 果。 前述洗淨液的純度及潔淨度，考慮對進行洗淨處理的 被洗淨物之污染的問題及製造成本而設定即可。例如積體 電路的製造製程使用本發明的洗淨液的情況下，含於該洗 淨液之金屬雜質爲0.1 ppb以下較理想。 此外，關於本發明的洗淨液之製造方法，無特別限制 ’可以傳統習知的方法製作。 -11 - 201042031 然後’說明使用本發明的洗淨液之洗淨方法。 適用本發明的洗淨液之被洗淨物，無特別限制，例如 單結晶矽、多結晶矽、非晶矽、熱矽氧化膜、無摻雜矽酸 鹽玻璃膜、磷摻雜矽酸鹽玻璃膜、硼摻雜矽酸鹽玻璃膜、 磷硼摻雜矽酸鹽玻璃膜、TEOS膜、電漿CVD氧化膜、矽 氮化膜、矽碳化膜、氧化矽碳化膜或氧化矽碳化氮化膜等 。而且亦可適用玻璃、石英、水晶、陶瓷等。此等可單獨 構成，亦可組合2種以上。 本發明的洗淨液，適合用於以硏磨步驟平坦化之被洗 淨物。作爲被洗淨物表面的硏磨方法無特別限制，可採用 傳統習知的各種方法。硏磨方法，可依被洗淨物的形狀、 作爲目的之硏磨精度而適當選擇。具體地，例如機械硏磨 、化學機械硏磨（CMP )等，本發明的洗淨液適合使用氧 化鈽糊漿之化學機械硏磨（CMP )。氧化铈糊漿係作爲硏 磨粒之氧化鈽分散於溶液中者。 作爲洗淨方法無特別限制，只要使洗淨液接觸被洗淨 物即可。更具體地，例如使被洗淨物浸漬於塡充於洗淨槽 的洗淨液中之浸漬處理方法。而且，於旋轉中的矽晶圓等 的被洗淨物上，吐出洗淨液，藉由吹拂進行洗淨處理之單 片式處理方法等。而且，於前述浸漬處理方法，可採用一 邊對洗淨液施加超音波之方法。再者，亦可適用一邊吹洗 淨液一邊藉由刷子洗淨之刷洗方法。而且，洗淨亦可進行 數次。於該情況，各洗淨操作可使用組成及其濃度相異的 洗淨液。 -12- 201042031 作爲洗淨時間無特別限制，依據附著於被洗淨物之氧 化姉的污染程度等適當設定。通常爲1〇分以下的範圍內 較理想，3分以下更理想。洗淨時間超過10分時，有被洗 淨物的表面被蝕刻，表面粗糙度增加的情形。 洗淨時的洗淨液之液溫爲30°C以下較理想，15〜25°C 更理想。超過30 °C時，因揮發成分的揮發而有洗淨液的組 成產生變化的情形。洗淨液的液溫調節，例如可使用PID 0 式溫度控制器。 前述洗淨液的蝕刻速率，液溫25 °C下爲10A/分以下 較理想，0〜5 A/分更理想。前述數値範圍之蝕刻速率對被 洗淨物爲單結晶矽、多結晶矽、熱矽氧化膜之情況更適合 。藉由蝕刻速率爲10A/分以下，可洗淨除去氧化鈽，同時 可期望抑制對被洗淨物之蝕刻。 而且，關於本發明的洗淨方法，前述洗淨處理後，依 據需要可進行藉由超純水等的洗滌劑之洗滌步驟。藉此， 〇 可防止洗淨液殘存於被洗淨物的表面。 實施例 以下，詳細說明該發明的較佳實施例。但是，該實施 例所記載的材料、調配量等，不受限於該特定的記載，該 發明的範圍不限於此等實施例，僅只是說明的例子。 (洗淨液的製作方法） 關於各實施例或比較例之洗淨液，係以下所示的原材 -13- 201042031 料的任一者適當調配而製作。亦即（1) 50重量％高純度 氟化氫酸（Stella-chemifa公司製）、（2) EL級36重量 %鹽酸（三菱化學公司製）、（3 ) E L級6 9重量％硝酸（ 三菱化學公司製）、（4) EL級97重量％硫酸（三菱化學 公司製）、（5 ) EL級86重量％磷酸（Kishida化學公司 製）、（6 )超純水的任一者依既定的混合比例調配而製 作。 (被洗淨物表面的殘渣殘留狀態的測定方法） 被洗淨物表面的氧化铈的固體物之殘渣狀態，係使用 TREX610-T ( Technos公司製）進行。亦即，在藉由洗淨 液之洗淨處理前後進行測定，確認藉由洗淨液的洗淨效果 (實施例1 ) 於本實施例，如表1所示，製作氟化氫濃度爲0.1重 量％，鹽酸濃度爲1 0重量％的洗淨液。 然後，對表面有TEOS成膜之直徑200mm的矽基板， 使用氧化鈽作爲硏磨粒進行化學機械硏磨，使用其作爲被 洗淨物。於該被洗淨物，藉由後述的殘渣殘留狀態的測定 ，確認1 000 X 1 09原子/cm2程度的氧化铈爲殘渣成分。 接著，塡充前述洗淨液於9 0L的洗淨液槽’洗淨液溫 度調節爲2 5。(：，使洗淨液溫度安定。使前述被洗淨物保持 於PFA樹脂製的矽基板保持構件上’於前述洗淨液槽中， -14- 201042031 浸漬1分鐘。浸漬後，連矽基板保持構件一起從洗淨液槽 撈起，浸漬於預先準備的容積90L的超純水洗漉槽，沖洗 附著於被洗淨物表面之洗淨液。然後，使被洗淨物乾燥， 再度進行殘渣殘留狀態的測定。除去性能的良好、不良， 於處理後粒子狀固形分量減少至8.5 χΙΟ9原子/cm2以下的 情況爲良好，而沒有減少至8 · 5 X 1 09原子/cm2以下的情況 爲不良。藉由洗淨液之洗淨處理前後的殘渣殘留狀態的測 0 定結果表示於下述表1。 (實施例2〜1 1 ) 於實施例2〜1 1，除改變如表1所示之洗淨液的組成 及濃度外，與前述實施例1同樣地製作各洗淨液。再者， 與前述實施例1同樣地進行藉由各洗淨液之洗淨處理等。 結果表示於下述表1。 〇 (比較例1〜9 ) 於比較例1〜9，除改變如表1所示之洗淨液的組成及 濃度外，與前述實施例1同樣地製作各洗淨液。再者，與 前述實施例1同樣地進行藉由各洗淨液之洗淨處理等。結 果表示於下述表1。 -15- 201042031 [表i] 被處理 物表面 氟化氫 酸濃度 其他酸 括来百 其他酸 濃度 粒子上固形分量 (铈成分)(x 1 〇9原子/咖2) 除去 性能 pH (%) (%) 處理前 處理後 實施例1 0.1 鹽酸 10 4800 <8.5 良好 <0 實施例2 0.1 硝酸 10 5200 <8.5 良好 <0 實施例3 0.1 硫酸 10 5500 <8.5 良好 <0 實施例4 0.1 磷酸 10 4600 <8.5 良好 1.7 實施例5 0.1 鹽酸 20 5100 <8.5 良好 <0 實施例ό 0.1 硝酸 20 5300 <8.5 良好 <0 實施例7 0.1 鹽酸 30 5400 <8.5 1好 <0 實施例8 0.5 鹽酸 10 4800 <8.5 良好 <0 實施例9 0.5 硝酸 10 5200 <8.5 良好 <0 實施例10 TEOS 膜 0.5 硫酸 10 5500 <8.5 良好 <0 實施例Π 0.5 磷酸 10 4600 <8.5 良好 1.6 比較例1 0.1 無 5200 515 不良 2.2 比較例2 0.5 _ 5200 515 不良 1.8 比較例3 0 鹽酸 10 4500 32 不良 <0 比較例4 0 硝酸 10 4400 45 不良 <0 比較例5 0 硫酸 10 5300 33 不良 <0 比較例6 0 磷酸 10 5700 60 不良 1.6 比較例7 0 鹽酸 20 5400 50 不良 <0 比較例8 0 硝酸 20 5200 65 不良 <0 比較例9 0 鹽酸 30 4900 52 不良 <0 由前述表1的結果得知，於使用關於本實施例1〜U 之洗淨液的情況，被洗淨物表面之鈽成分的固形分量減少 至8.5χ1 09原子/cm2以下，得知藉此對氧化鈽的洗淨除去 之效果佳。 另一方面，關於比較例1〜9，铈成分的固形分量之減 少量低，確認對氧化鈽的洗淨除去之效果低。 -16- 201042031 (實施例1 2 ) 於本實施例，除使用具有多晶矽膜成膜之直徑200mm 的矽基板，作爲被洗淨物，且如表2所示改變洗淨液的組 成及濃度外，與前述實施例1同樣地製作各洗淨液。再者 ，與前述實施例1同樣地進行藉由各洗淨液之洗淨處理等 。除去性能的良好、不良，於處理後粒子狀固形分量減少 (〇 至8.5 XI 09原子/cm2以下的情況爲良好，而沒有減少至 8.5 X 109原子/cm2以下的情況爲不良。結果表示於下述表2 (實施例1 3〜2 2 ) 於實施例13〜22，除改變如表2所示之洗淨液的組成 及濃度外，與前述實施例12同樣地製作各洗淨液。再者 ’與前述實施例12同樣地進行藉由各洗淨液之洗淨處理 〇 等。結果表示於下述表2。 (比較例1 〇〜1 8 ) 於實施例10〜18，除改變如表2所示之洗淨液的組成 及濃度外，與前述實施例12同樣地製作各洗淨液。再者 ，與前述實施例12同樣地進行藉由各洗淨液之洗淨處理 等。結果表示於下述表2。 -17- 201042031 [表2] 被處理 氟化氫酸 其他酸 其他酸 粒子上固形分量(铈成 除去 pH 物表面 濃度(％) 麵 濃度(％) 分)(x 1 〇9 原子/cm2) 性能 處理前 處理後 實施例12 0.1 鹽酸 10 4600 <8.5 良好 <0 實施例13 0.1 硝酸 10 5300 <8.5 良好 <0 實施例14 0.1 硫酸 10 5600 <8.5 良好 <0 實施例15 0.1 磷酸 10 4900 <8.5 良好 1.7 實施例16 0.1 鹽酸 20 4900 <8.5 良好 <0 實施例17 0.1 硝酸 20 5000 <8.5 良好 <0 實施例18 0.1 鹽酸 30 6400 <8.5 良好 <0 實施例19 0.5 鹽酸 10 5800 <8.5 良好 <0 實施例20 0.5 硝酸 10 4800 <8.5 良好 <0 實施例21 多晶矽膜 0.5 硫酸 10 6500 <8.5 良好 <0 實施例22 0.5 磷酸 10 6700 <8.5 良好 1.6 比較例10 0.1 4E _ 6600 6300 不良 2.2 比較例11 0.5 姐 yws _ 4900 4800 不良 1.8 比較例12 0 鹽酸 10 4800 4300 不良 <0 比較例13 0 硝酸 10 4900 4200 不良 <0 比較例14 0 硫酸 10 5400 4600 不良 <0 比較例15 0 磷酸 10 4500 3700 不良 1.6 比較例16 0 鹽酸 20 5200 4500 不良 <0 比較例17 0 硝酸 20 4900 4000 不良 <0 比較例18 0 鹽酸 30 5200 4500 不良 <0 由前述表2的結果得知，於使用關於本實施例12〜22 之洗淨液的情況，被洗淨物表面之姉成分的固形分量減少 至8.5 χΙΟ9原子/cm2以下，得知藉此對氧化鈽的洗淨除去 之效果佳。 另一方面，關於比較例10〜18，铈成分的固形分量之 減少量低，確認對氧化鈽的洗淨除去之效果低。 -18-201042031 VI. Description of the Invention: [Technical Field] The present invention relates to a cleaning solution for removing cerium oxide from a cerium oxide-attached material and a cleaning method using the same; The high performance of the ultra-large integrated circuit (ULSI) is the result of the miniaturization of circuit design. In order to form a very fine circuit structure of the nanometer grade, many manufacturing steps that have not been subjected to the manufacturing technology are required. In particular, as a final step in forming a fine structure on a semiconductor substrate, an exposure/lithography step using an optical means is used. In order to fabricate the structure, the flatness of the same uniform surface of the conjugate plate on the surface of the semiconductor substrate is inseparable. That is, in the case where the substrate is not excellent in appearance, a focused portion is generated on the surface of the substrate, and a desired fine structure cannot be produced in the unfocused portion, and the growth is reduced. Further, as the miniaturization continues to progress, the flatness tolerance range becomes smaller, and the flatness of the substrate surface is further improved. Further, in addition to the flattening requirement, the step time for improving the production is required to be shortened. Therefore, in addition to the processing of fine processing, a technique for speeding up the steps is required. From the so-called technical technique for ensuring flatness, chemical mechanical honing is generally performed (in the CMP step, using granular honing particles, high-speed, and washable methods) The important step is to make the subtle point, and the efficiency of the degradation of the flat focus portion of the base surface is required to be the efficiency of the external precision, background, for CMP). Semiconductor base 201042031 Honing (flattening) of the surface of the board. In the aforementioned c Μ P step, for example, a technique using cerium oxide paste is used. However, it is a step of washing and removing the cerium oxide paste which remains as a residue due to the CMP step. The cleaning agent described in the following Patent Document 1 for the purpose of removing particles, organic impurities, and metal impurities, for example, is a cleaning agent. In addition, for example, the cleaning liquid for a semiconductor substrate described in Patent Document 2 below is used for the purpose of removing particles on a semiconductor substrate. On the other hand, in the CMP step, chemical mechanical honing using cerium oxide as cerium particles was also carried out. However, the above-mentioned detergent has a problem that it is difficult to remove the residue of cerium oxide. As a result, it becomes a main cause of a decrease in productivity of a semiconductor device. CITATION LIST OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION [Technical Problem] The present invention is to provide a surface-attached cerium oxide to be washed. The net object is a cleaning solution which dissolves cerium oxide into cerium ions and can be washed and removed, and a washing method using the same. [Means for Solving the Problem] In order to solve the above-mentioned conventional problems, the inventors of the present invention reviewed the cleaning liquid and the cleaning method using the same. As a result, it was found that at least one acid and water washing liquid containing fluorine-6-201042031 hydrogen and a group selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, iodic acid, and hydrocyanic acid can be washed. The cerium oxide is removed neatly, thus completing the present invention. In other words, the cleaning liquid of the present invention is a cleaning liquid for removing cerium oxide, which is characterized by containing hydrogen fluoride and selected from hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, iodic acid, and bromine. At least one acid composed of hydrogenation acid and water are formed, and the cerium oxide is dissolved and removed. The hydrogen fluoride solution can dissolve cerium oxide into cerium ions due to the strength of its oxidizing power. However, since the dissolved cesium ions are again attached to the surface of the object to be cleaned with impurities, it is still difficult to remove cerium oxide. On the other hand, in the case where the above-mentioned acid is used as the cleaning liquid, since the oxidizing power of these acids is weak, it is difficult to dissolve the cerium oxide into cerium ions and it is impossible to remove them. However, as described above, the hydrogen fluoride and the acid cleaning liquid 'hydrogen fluoride are combined to dissolve the cerium oxide into the cleaning liquid, and the ceric acid is removed from the surface of the object to be washed. . That is, in the case of the above-described cleaning liquid, the cerium oxide which is difficult to remove by the conventional cleaning liquid can be washed away. Thereby, for example, the cleaning after the chemical mechanical honing step using the cerium oxide as the semiconductor substrate of the honing particles can effectively remove the cerium oxide by using the cleaning liquid of the present invention, and it is desired to improve the production of the semiconductor device. effectiveness. In the above configuration, the concentration of the hydrogen fluoride is in the range of 0.001 to 20% by weight, and the concentration of the acid is preferably in the range of 0.0001 to 50% by weight. When the concentration of the hydrogen fluoride is 0.001% by weight or more, it is possible to prevent the deterioration of the solubility of cerium oxide by 201042031, and to prevent the object to be etched by being 20% by weight or less. Further, 'the concentration of the acid listed above is 0.02% by weight or more, and the performance of removing cerium oxide from the object to be washed can be ensured, and at the same time, the solubility of cerium oxide can be prevented from being lowered by 50% by weight or less. . Further, in the cleaning method of the present invention, in order to solve the above-mentioned problems, the cleaning method of the cleaning liquid described above is used, and the cerium-attached material to be washed is brought into contact with the cleaning liquid. The cerium oxide is dissolved into cerium ions and removed. The cleaning liquid of the present invention is brought into contact with the object to which the cerium oxide is attached, and the cerium oxide is dissolved in the cleaning liquid, and is prevented from adhering to the surface of the object to be washed and removed. Thereby, for example, in the manufacturing process of the semiconductor device, even if a chemical mechanical honing step using yttrium oxide as the semiconductor substrate of the honing particles is used, the residue of the cerium oxide can be removed from the surface of the semiconductor substrate, and the productivity of the semiconductor device can be improved. . In the above method, the etching rate of the cleaning liquid is preferably 1 ο A/min or less for the etch rate of the object to be washed at a liquid temperature of 25 °C. By the cleaning liquid used in the cleaning method of the present invention, the etching rate of the object to be washed is suppressed to 10 A/min or less, and etching of the object to be washed can be prevented. As a result, the increase in the surface roughness of the object to be washed can be suppressed, and the cerium oxide can be removed by washing. Further, in the above method, the liquid temperature at the time of washing the cleaning liquid is preferably 30 ° C or lower. Further, in the above method, it is preferred that the above-mentioned washed material is chemically honed by cerium oxide paste into -8-201042031. [Effects of the Invention] The present invention can achieve the effects described below by the means described above. That is, according to the present invention, it is possible to effectively remove and remove cerium oxide which is difficult in the conventional acid cleaning liquid. As a result, for example, in the process of manufacturing a semiconductor device, even if a chemical mechanical honing (CMP) step using a ruthenium oxide as a semiconductor substrate of honing particles is used, the oxide residue can be removed from the surface of the semiconductor substrate, and the semiconductor can be improved. The productivity of the device. [Embodiment] The cleaning liquid of the present invention will be described below. The cleaning solution of the present invention comprises at least one acid containing hydrogen fluoride and a group selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, iodic acid, and hydrocyanic acid, and water. Further, the cleaning liquid of the present invention is preferably constituted by the above-exemplified acid as a main component. Here, for example, in the case of a cleaning liquid formed by a combination of hydrogen peroxide and the above-mentioned acid, it is difficult for the cleaning liquid to dissolve cerium oxide into cerium ions, and it is impossible to wash and remove cerium oxide. In the present invention, cerium oxide is dissolved into cerium ions by oxidizing power by containing hydrogen fluoride in the cleaning liquid. Further, the cleaning liquid formed of the above-mentioned acid alone is difficult to dissolve the cerium oxide by itself, and it is more difficult to wash and remove the immersed material. However, by using these acids and hydrogen fluoride, not only the cerium oxide ions are dissolved in the cleaning liquid, but also removed from the surface of the object to be washed. That is, the cleansing solution of the present invention can be washed and removed by a combination of hydrogen fluoride and the aforementioned acid. Further, cerium ions refer to Ce3+, Ce4+, hydrates thereof or the like. The concentration of the hydrogen fluoride in the entire cleaning solution is preferably in the range of 0.001 to 20% by weight, more preferably in the range of 0.01 to 5% by weight. When the concentration of hydrogen fluoride is less than 0.001% by weight, the solubility of cerium oxide dissolved in cerium ions is lowered, and as a result, the cleaning effect of cerium oxide is lowered, which is not preferable. On the other hand, when the concentration of hydrogen fluoride exceeds 20% by weight, the object to be cleaned is etched, and the surface roughness thereof may increase. Further, after the washing treatment, when the hydrogen fluoride in the washing liquid to be drained is detoxified, the required cost and time may increase. Among the above-exemplified acids, hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid is preferred in the present invention. In the case of such an acid, the washing solution in which the cerium ions are dissolved does not remain on the surface of the object to be washed and is easily removed. The concentration of at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, iodic acid, and hydrogen bromide is preferably in the range of 0.001 to 50% by weight, and 0.001 to 20% by weight. The range of % is more ideal. When the concentration of the acid is less than 0.001% by weight, the removal performance of cerium oxide removed from the object to be washed may be lowered. On the other hand, when it exceeds 50% by weight, when the acid in the washing liquid to be drained is detoxified after the washing treatment, the cost and time required may increase. Further, the volatile component is evaporated, the composition of the cleaning liquid changes, and the stable washing treatment becomes difficult. A surfactant may also be added to the cleaning solution of the present invention. Thereby, the surface tension of the low-washing liquid is lowered by -10-201042031, and the wettability to the surface of the object to be washed is improved. As a result, the washed matter can be uniformly washed and removed in a wider range, and productivity can be expected to be improved. The surfactant is not particularly limited, and examples thereof include an anionic surfactant such as an aliphatic carboxylic acid or a salt thereof. Further, a nonionic surfactant such as a polyvinyl alcohol alkyl ether, a cationic surfactant such as an aliphatic amine or a salt thereof may be used. The amount of the surfactant to be added is suitably in the range of 0.001 to 0.1% by weight in the range of 0 to 003 to 0.05% by weight. By adding an surfactant, cracking of the surface of the washed treated object can be suppressed. Further, the wettability of the object to be washed is improved, and the uniformity of the in-plane washing effect can be expected. However, when the amount of addition is less than 〇 〇 〇 1% by weight, the surface tension of the cleaning liquid is not sufficiently lowered, and the effect of improving the wettability is insufficient. Further, when the amount added is more than 0.1% by weight, not only the effect of balancing the effect is not obtained, but also the defoaming property is deteriorated, and bubbles are adhered to the surface of the object to be washed, and washing unevenness may occur. pH The pH of the cleaning solution is preferably 2 or less, more preferably 1 or less. By the pH of 2 or less, the dissolution state of the cerium ions can be stabilized, and the washing effect can be improved. The purity and cleanliness of the cleaning liquid may be set in consideration of the problem of contamination of the washed matter subjected to the washing treatment and the manufacturing cost. For example, when the cleaning liquid of the present invention is used in the manufacturing process of the integrated circuit, the metal impurities contained in the cleaning liquid are preferably 0.1 ppb or less. Further, the method for producing the cleaning liquid of the present invention is not particularly limited, and can be produced by a conventionally known method. -11 - 201042031 Next, the cleaning method using the cleaning liquid of the present invention will be described. The washing liquid to which the cleaning liquid of the present invention is applied is not particularly limited, and is, for example, a single crystal ruthenium, a polycrystalline ruthenium, an amorphous ruthenium, a hot ruthenium oxide film, an undoped silicate glass film, a phosphorus-doped ruthenate. Glass film, boron doped tellurite glass film, phosphorous boron doped tellurite glass film, TEOS film, plasma CVD oxide film, tantalum nitride film, tantalum carbonized film, tantalum carbonized film or tantalum carbonitride Membrane and the like. It is also applicable to glass, quartz, crystal, ceramics, and the like. These may be configured separately or in combination of two or more. The cleaning liquid of the present invention is suitable for use in a laundry which is flattened by a honing step. The honing method as the surface of the object to be washed is not particularly limited, and various conventional methods can be employed. The honing method can be appropriately selected depending on the shape of the object to be washed and the honing precision for the purpose. Specifically, for example, mechanical honing, chemical mechanical honing (CMP), etc., the cleaning liquid of the present invention is suitably used for chemical mechanical honing (CMP) of cerium oxide paste. The cerium oxide paste is used as a cerium oxide of cerium abrasive grains dispersed in a solution. The washing method is not particularly limited as long as the washing liquid is brought into contact with the laundry. More specifically, for example, an immersion treatment method in which the object to be washed is immersed in a washing liquid filled in the washing tank. In addition, a cleaning treatment is performed on the object to be washed such as a crucible wafer, and a single-piece processing method in which the cleaning treatment is performed by blowing is performed. Further, in the above immersion treatment method, a method of applying ultrasonic waves to the cleaning liquid may be employed. Further, a brushing method of washing with a brush while purging the liquid is also applicable. Moreover, washing can be performed several times. In this case, a washing liquid having a composition and a different concentration can be used for each washing operation. -12- 201042031 The washing time is not particularly limited, and is appropriately set depending on the degree of contamination of the cerium oxide attached to the object to be washed. It is usually in the range of 1 minute or less, and more preferably 3 minutes or less. When the washing time exceeds 10 minutes, the surface of the object to be cleaned is etched, and the surface roughness is increased. The liquid temperature of the washing liquid at the time of washing is preferably 30 ° C or less, and more preferably 15 to 25 ° C. When the temperature exceeds 30 °C, the composition of the cleaning liquid changes due to the volatilization of the volatile component. For the liquid temperature adjustment of the cleaning liquid, for example, a PID 0 type temperature controller can be used. The etching rate of the cleaning liquid is preferably 10 A/min or less at a liquid temperature of 25 ° C, and more preferably 0 to 5 A/min. The etching rate in the above range is more suitable for the case where the object to be washed is a single crystal germanium, a polycrystalline germanium or a hot tantalum oxide film. By removing the yttrium oxide by an etching rate of 10 A/min or less, it is desirable to suppress etching of the object to be washed. Further, in the cleaning method of the present invention, after the washing treatment, a washing step by detergent such as ultrapure water can be carried out as needed. Thereby, 〇 can prevent the cleaning liquid from remaining on the surface of the object to be washed. EXAMPLES Hereinafter, preferred embodiments of the invention will be described in detail. However, the materials, the blending amounts, and the like described in the examples are not limited to the specific description, and the scope of the invention is not limited to the examples, and is merely illustrative examples. (Manufacturing method of the cleaning liquid) The cleaning liquid of each of the examples or the comparative examples was prepared by appropriately blending any of the materials -13 - 201042031 shown below. That is, (1) 50% by weight of high-purity hydrogen fluoride acid (manufactured by Stella-Chemifa Co., Ltd.), (2) EL grade 36% by weight hydrochloric acid (manufactured by Mitsubishi Chemical Corporation), (3) EL grade 69% by weight of nitric acid (Mitsubishi Chemical Co., Ltd. (4) EL grade 97% by weight sulfuric acid (manufactured by Mitsubishi Chemical Corporation), (5) EL grade 86% by weight phosphoric acid (Kishida Chemical Co., Ltd.), and (6) ultrapure water according to a predetermined mixing ratio Made with blending. (Measurement Method of Residual State of Residue on Surface of Object to Be Washed) The state of residue of solid cerium oxide on the surface of the object to be washed was carried out using TREX610-T (manufactured by Technos Co., Ltd.). That is, the measurement was performed before and after the washing treatment by the cleaning liquid, and the washing effect by the cleaning liquid (Example 1) was confirmed. In the present example, as shown in Table 1, the hydrogen fluoride concentration was 0.1% by weight. A washing solution having a hydrochloric acid concentration of 10% by weight. Then, a ruthenium substrate having a diameter of 200 mm having a TEOS film formed on the surface thereof was subjected to chemical mechanical honing using yttrium oxide as a honing granule, and was used as a immersion. In the object to be washed, it was confirmed that the cerium oxide of about 1 000 X 1 09 atoms/cm 2 was a residue component by the measurement of the residual state of the residue described later. Next, the washing liquid was added to the washing liquid tank of 90 liters, and the temperature of the washing liquid was adjusted to 2 5 . (: The temperature of the cleaning liquid is stabilized. The immersed material is held on the ruthenium substrate holding member made of PFA resin in the cleaning liquid tank, and immersed for 1 minute at -14 to 201042031. The holding member is picked up from the cleaning liquid tank, immersed in a 90 L ultra-pure water washing tank prepared in advance, and rinsed with the washing liquid adhering to the surface of the object to be washed. Then, the object to be washed is dried, and the residue is again subjected to residue. The measurement of the residual state is good and the removal performance is good, and the case where the particulate solid content is reduced to 8.5 χΙΟ 9 atoms/cm 2 or less after the treatment is good, and the case where the particle solid content is not reduced to 8.5 × 1 09 atoms/cm 2 or less is bad. The results of the measurement of the residual state of the residue before and after the washing treatment of the cleaning liquid are shown in the following Table 1. (Examples 2 to 1 1) In the examples 2 to 1 1, the change was as shown in Table 1. In addition to the composition and the concentration of the cleaning liquid, each of the cleaning liquids was prepared in the same manner as in Example 1. Further, in the same manner as in Example 1, the cleaning treatment by the respective cleaning liquids was performed. Table 1. 〇 (Comparative Examples 1 to 9) In each of Examples 1 to 9, each washing liquid was prepared in the same manner as in Example 1 except that the composition and concentration of the washing liquid shown in Table 1 were changed. Further, in the same manner as in Example 1, each washing was carried out. The washing liquid of the cleaning liquid, etc. The results are shown in the following Table 1. -15- 201042031 [Table i] Hydrofluoric acid concentration on the surface of the treated object Other acid includes the solid component (铈 component) of the other acid concentration particles (x 1 〇9 atom/coffee 2) Removal performance pH (%) (%) After treatment treatment Example 1 0.1 Hydrochloric acid 10 4800 < 8.5 Good <0 Example 2 0.1 Nitric acid 10 5200 < 8.5 Good <0 Example 3 0.1 sulfuric acid 10 5500 < 8.5 good <0 Example 4 0.1 Phosphoric acid 10 4600 < 8.5 Good 1.7 Example 5 0.1 Hydrochloric acid 20 5100 < 8.5 Good <0 Example ό 0.1 Nitric acid 20 5300 < 8.5 Good < 0 Example 7 0.1 Hydrochloric acid 30 5400 < 8.5 1 Good <0 Example 8 0.5 Hydrochloric acid 10 4800 < 8.5 Good <0 Example 9 0.5 Nitric acid 10 5200 < 8.5 Good <0 Example 10 TEOS film 0.5 sulfuric acid 10 5500 < 8.5 good <0 Example Π 0.5 Phosphoric acid 10 46 00 < 8.5 Good 1.6 Comparative Example 1 0.1 No 5200 515 Bad 2.2 Comparative Example 2 0.5 _ 5200 515 Poor 1.8 Comparative Example 3 0 Hydrochloric acid 10 4500 32 Poor <0 Comparative Example 4 0 Nitric acid 10 4400 45 Poor <0 Comparative Example 5 0 Sulfuric acid 10 5300 33 Poor <0 Comparative Example 6 0 Phosphoric acid 10 5700 60 Poor 1.6 Comparative Example 7 0 Hydrochloric acid 20 5400 50 Poor <0 Comparative Example 8 0 Nitric acid 20 5200 65 Poor <0 Comparative Example 9 0 Hydrochloric acid 30 4900 52 Poor <0 From the results of Table 1 above, in the case of using the cleaning liquids of the present Examples 1 to U, the solid content of the bismuth component on the surface of the object to be washed was reduced to 8.5 χ 1 09 atoms/cm 2 Hereinafter, it is found that the effect of washing and removing cerium oxide is good. On the other hand, in Comparative Examples 1 to 9, the decrease in the solid content of the cerium component was small, and it was confirmed that the effect of washing and removing cerium oxide was low. -16- 201042031 (Example 1 2) In this example, except that a crucible substrate having a diameter of 200 mm formed by a polycrystalline germanium film was used as a material to be washed, and the composition and concentration of the cleaning liquid were changed as shown in Table 2 Each of the cleaning liquids was prepared in the same manner as in the above Example 1. Further, in the same manner as in the first embodiment, the washing treatment by the respective cleaning liquids or the like is performed. The removal performance was good and poor, and the particulate solid content decreased after the treatment (the case of 〇 8.5 XI 09 atoms/cm 2 or less was good, and the case where it was not reduced to 8.5 X 109 atoms/cm 2 or less was bad. The result is shown below. Table 2 (Examples 1 to 3 2) In each of Examples 13 to 22, each of the cleaning liquids was prepared in the same manner as in Example 12 except that the composition and concentration of the cleaning liquid shown in Table 2 were changed. In the same manner as in the above-described Example 12, the cleaning treatment of each of the cleaning liquids was carried out, etc. The results are shown in Table 2 below. (Comparative Example 1 〇~1 8 ) In Examples 10 to 18, except for In addition to the composition and the concentration of the cleaning liquid shown in Table 2, each of the cleaning liquids was prepared in the same manner as in Example 12. Further, in the same manner as in the above-described Example 12, the cleaning treatment by the respective cleaning liquids was performed. The results are shown in the following Table 2. -17- 201042031 [Table 2] The solid content of the other acid particles of the hydrogen fluoride acid treated (the surface concentration (%) of the pH-removed surface (%)) (x 1 〇 9 atom/cm2) Performance treatment before treatment Example 12 0.1 Hydrochloric acid 10 4600 < ; 8.5 Good <0 Example 13 0.1 Nitric acid 10 5300 < 8.5 Good <0 Example 14 0.1 Sulfuric acid 10 5600 < 8.5 Good <0 Example 15 0.1 Phosphoric acid 10 4900 < 8.5 Good 1.7 Example 16 0.1 Hydrochloric acid 20 4900 < 8.5 Good <0 Example 17 0.1 Nitric acid 20 5000 < 8.5 Good <0 Example 18 0.1 Hydrochloric acid 30 6400 < 8.5 Good <0 Example 19 0.5 Hydrochloric acid 10 5800 < 8.5 Good < 0 Example 20 0.5 Nitric acid 10 4800 < 8.5 Good <0 Example 21 Polycrystalline ruthenium film 0.5 Sulfuric acid 10 6500 < 8.5 Good <0 Example 22 0.5 Phosphoric acid 10 6700 < 8.5 Good 1.6 Comparative Example 10 0.1 4E _ 6600 6300 Bad 2.2 Comparative Example 11 0.5 Sister yws _ 4900 4800 Poor 1.8 Comparative Example 12 0 Hydrochloric acid 10 4800 4300 Poor <0 Comparative Example 13 0 Nitric acid 10 4900 4200 Poor <0 Comparative Example 14 0 Sulfuric acid 10 5400 4600 Poor < 0 Comparative Example 15 0 Phosphoric acid 10 4500 3700 Poor 1.6 Comparative Example 16 0 Hydrochloric acid 20 5200 4500 Poor <0 Comparative Example 17 0 Nitric acid 20 4900 4000 Poor <0 Comparative Example 18 0 Hydrochloric acid 30 5200 4500 Poor <0 As a result of the above Table 2, it was found that, in the case of using the cleaning liquids of Examples 12 to 22, the solid content of the cerium component on the surface of the object to be washed was reduced to 8.5 χΙΟ 9 atoms/cm 2 or less, and it was found that the oxidizing was performed by this. The effect of washing and removing the cockroach is good. On the other hand, in Comparative Examples 10 to 18, the amount of reduction in the solid content of the cerium component was low, and it was confirmed that the effect of washing and removing cerium oxide was low. -18-