201235464 六、發明說明： 【發明所屬之技術領域】 本發明係有關對已附著氧化铈之被洗淨物，可將該氧 化鈽洗淨去除之洗淨液，及使用該洗淨液之洗淨方法。 【先前技術】 爲達到大型積體電路（ULSI)的高性能化之目的，電路 設計的微細化持續進展中。爲形成經微細化至奈米等級之 非常微細的電路構造，許多製造步驟中需要至今仍未適用 之新的製造技術。 尤其’於半導體菡板上形成微細構造之最重要的步驟 中’有使用光學技術之曝光、顯影步驟。爲製作此微細構 造’於半導體基板的表面上相同、均一地聚焦，與基板表 面的平坦性密切相關。即，基板表面的平坦性不佳時，將 於基板表面上產生聚焦部分與未聚焦部分，未聚焦部分無 法形成期望的微細構造，造成生產性大幅下降。再者，隨 著微細化之進展有關平坦性之可容許範圍將縮小，進一步 提高基板表面的平坦化要求。 再者’除了平坦化的要求之外，亦有爲達到提高生產 效率之目的縮短步驟時間之要求。因此，需要除了微細加 工的加工精密度之外亦可使步驟商速化之技術。由此技術 上的背景’一般進行化學機械硏磨（C Μ P)作爲確保平坦性 之技術。CMP係供給含有顆粒狀的硏磨粒之硏磨劑（硏磨 漿）的同時使用硏磨墊將半導體基板表面硏磨（平坦化）。 201235464 上述CMP中，廣泛使用二氧化矽硏磨漿作爲硏磨劑 ，但亦使用二氧化姉硏磨漿，與二氧化矽硏磨漿的情況相 同，需要爲將殘留於基板表面之殘渣去除之洗淨步驟。洗 淨步驟中所使用之洗淨劑，有例如以下之提案。 專利文獻1揭示含有酸、還原劑及氟離子3種成分之 洗淨藥液。 專利文獻2揭示由氟化氫與硫酸或硝酸或磷酸所構成 之洗淨液。 然而，以往的洗淨液即使可去除氧化鈽的殘渣，因其 以酸爲主要成分，故有易將各種金屬材料腐蝕之問題。例 如，半導體基板上的金屬膜因腐蝕而溶解時，金屬膜的膜 厚度減少金屬膜的表面電阻値將變大。由此造成積體電路 上配線的電阻値變大消費電力增加故不佳。 [先前技術文獻] [專利文獻] [專利文獻1 ]特開2 0 0 4 - 5 9 4 1 9號公報 [專利文獻2]特開2000-140778號公報 【發明內容】 [發明欲解決之課題] 本發明的目的係提供對已於表面附著氧化鈽之被洗淨 物’可將該氧化铈溶解爲鈽離子以將其洗淨去除，且不易 腐蝕各種金屬材料之洗淨液，及使用該洗淨液之洗淨方法 -6 - 201235464 [解決課題之手段] 本發明人爲解決上述以往問題，針對洗淨液及使用該 洗淨液之洗淨方法進行硏究。結果發現藉由使用含有氟化 氫與特定銨鹽之洗淨液，可將殘留於被洗淨物表面之氧化 鈽有效率地洗淨去除，完成本發明。 即’本發明係有關一種洗淨液，其係將殘留於被洗淨 物表面之氧化姉去除之洗淨液，其特徵係含有 (1 )氟化氫，與 (2 )至少1種選自由氯化銨、硝酸銨、硫酸銨、氯化四 甲銨、硝酸四甲銨、及硫酸四甲銨所構成之群組之銨鹽。 藉由使洗淨液中含有氟化氫，可使氧化鈽溶解爲铈離 子’但因已溶解之铈離子作爲雜質再次附著於被洗淨物的 表面，結果難以將铈成分去除。本發明人發現藉由使洗淨 液中共同含有氟化氫與特定的鉸鹽，可使已溶解之銨離子 以溶解狀態安定於洗淨液中，可有效率地自被洗淨物表面 去除。再者’本發明之洗淨液不若以往的洗淨液以硫酸、 硝酸、或磷酸等酸爲主要成分，故可抑制各種金屬材料之 腐蝕。另外，姉離子係指Ce3+、Ce4+、該等的水合物、或 該等的錯離子。 洗淨液中的氟化氫濃度以0.001〜5重量％爲佳。氟化 氫濃度未達0.001重量％時，氧化铈的溶解性能有下降之 傾向。另一方面，超過5重量％時，被洗淨物將被鈾刻或 201235464 腐蝕，以硏磨使其平坦化之被洗淨物的表面粗糙度有增大 之傾向。再者’洗淨處理後’將成爲排水之洗淨液中的氟 化氫無害化時，其所需費用及時間將增加° 洗淨液中上述銨鹽的濃度以ο.1-20重量％爲佳。上述 銨鹽的濃度未達0.1重量％時’難以使已溶解之銨離子以 溶解狀態安定於洗淨液中’有難以將鈽成分自被洗淨物表 面洗淨去除之傾向。另一方面’超過20重量％時’氧化 铈的溶解性能將下降，有因析出物之產生難以維持溶液的 性質而於洗淨時成爲不良的原因之傾向。 上述洗淨液以含有界面活性劑爲佳。藉由使洗淨液中 含有界面活性劑，降低洗淨液的表面張力’可提昇對被洗 淨物表面之浸濕性。藉此，可於被洗淨物表面的大範圍中 使洗淨去除效果均一化，故可望提昇生產性。 再者，本發明係有關一種洗淨方法，其係藉由使洗淨 液與已附著氧化铈之被洗淨物表面接觸，將氧化铈溶解爲 铈離子以將其去除之洗淨方法，其特徵係使用上述洗淨液 之含有 (1 )氟化氫，與 (2)至少1種選自由氯化銨、硝酸銨、硫酸銨、氯化四 甲銨、硝酸四甲銨、及硫酸四甲銨構成之群組之銨鹽 之洗淨液。 上述洗淨方法中，洗淨液中的氟化氫濃度以0.001〜5 重量％爲佳，上述銨鹽的濃度以0 · 1〜2 0重量％爲佳。其理 由如同上述。 -8 - 201235464 再者’上述洗淨方法中，洗淨液以含有界面活性劑爲 佳。其理由如同上述。 再者’上述洗淨方法適用於被洗淨物爲半導體基板、 玻璃基板、陶瓷基板、石英基板、或水晶基板時。 [發明效果] 藉由本發明’可有效率地將殘留於使用含有氧化铈之 硏磨劑硏磨之被洗淨物表面之氧化铈洗淨去除，且具有不 易腐蝕各種金屬材料之優點。因此，於例如半導體裝置的 製造程序中’可有效率地將氧化鈽的殘渣自硏磨後的半導 體基板洗淨去除，可提昇半導體裝置的生產性。再者，因 可抑制半導體基板上的金屬材料及構成半導體裝置之金屬 材料之腐蝕，故可提昇半導體裝置的性能。 【實施方式】 針對關於本發明之洗淨液的實施方式，說明如下。 本發明之洗淨液係含有（1 )氟化氫，與（2 )至少1 種選自由氯化銨、硝酸銨、硫酸銨、氯化四甲銨、硝酸四 甲銨、及硫酸四甲銨構成之群組之銨鹽，適用於使用含有 氧化鈽作爲硏磨粒之硏磨劑（硏磨漿）將殘留於經硏磨之被 洗淨物表面之氧化铈洗淨去除時。尤其，適用於使用氧化 鈽硏磨漿將殘留於經化學機械硏磨（CMP)之被洗淨物表面 之氧化铈洗淨去除時， 洗淨液中的氟化氫濃度以0.001〜5重量％爲佳’ -9- 201235464 0.001〜2重量％較佳。藉由降低氟化氫濃度，可有效率地 將氧化铈洗淨去除，同時抑制被洗淨物表面的材料之蝕刻 、腐蝕。 洗淨液中上述銨鹽的濃度以0.1〜20重量％爲佳， 0.1〜1 0重量％較佳，0 · 1 ~ 5重量％更佳。藉由降低銨鹽濃 度，可於藥液準備階段中節省資源、節省成本。具體而言 /可調製已濃縮成分濃度之洗淨液原液，再將該原液於洗 淨處理前以水等稀釋爲上述濃度之洗淨液。藉此，降低實 質上與洗淨液之製造或對運送用容器之塡充相關之資源或 成本、與已塡充至運送用容器之洗淨液之運送相關之資源 或成本，換言之，可提昇生產效率。 本發明之洗淨液中，上述以外之成分以水爲主要成分 爲佳，但含有水以外之成分亦可。可提及的有例如界面活 性劑、鉗合劑、pH値調整劑、及有機溶劑等。但，使用 此等時必須考量對洗淨裝置的有機成分之耐受性、廢棄時 的成本、及使用時的危險性等。 本發明之洗淨液以含有界面活性劑爲佳。界面活性劑 無特殊限制，可提及的有，例如脂肪族羧酸或其鹽等陰離 子型界面活性劑、聚乙二醇烷基醚等非離子型界面活性劑 、脂肪族胺或其鹽等陽離子型界面活性劑等。 界面活性劑的添加量以於0.001〜0.1重量％的範圍內 爲佳，以於0.003~0.05重量％的範圍內爲較佳。藉由添加 界面活性劑，可抑制已施以洗淨處理之被洗淨物表面的粗 糙。對被洗淨物之浸濕性進一步獲得改善，可望達到面內 -10- 201235464 中洗淨效果的均一性。然而，添加量未達0.001重量％時 ，洗淨液的表面張力無法充分下降’故有浸濕性的提昇效 果不充分之情形。再者，添加量超過〇. 1重量％時’不僅 無法獲得相對應之效果，甚至有消泡性惡化，泡沫附著於 被洗淨物表面，產生洗淨不均之情形。 上述洗淨液的純度及清淨度係以考量對進行洗淨處理 之被洗淨物污染的問題及製造成本設定爲佳。例如，於積 體電路的製造程序中使用本發明之洗淨液時，該洗淨液所 含有的金屬雜質以〇. 1 ppb以下爲佳。 本發明之洗淨液可藉由以任意順序混合氟化氫、上述 銨鹽、及其他任意成份調製而成。或者，混合可將上述各 種成分合成之化合物作爲原料，於最後調製成上述成分及 濃度的洗淨液亦可。具體而言，藉由混合氟化氫、硫酸、 氨與水，可調製成本發明之洗淨液。即，藉由硫酸與氨中 和，生成硫酸銨。再者，藉由混合例如氟化銨、硫酸與氨 ，可調製成本發明之洗淨液。 本發明之洗淨液於相當於使用階段之洗淨階段中形成 上述組成即可，針對準備階段的方式無任何限制。例如， 亦可調製成至使用場所爲止爲經濃縮之洗淨液原液，於使 用前稀釋調製成本發明之洗淨液。或例如，亦可個別準備 各成分，於使用前混合調製成本發明之洗淨液。 本發明之洗淨液的使用溫度無任何限制。實際應用上 ’以於有用的溫度區域之常溫中使用爲佳。再者，根據洗 淨條件，藉由例如以低於常溫1 0 °c之溫度進行洗淨，可 -11 - 201235464 抑制洗淨以外的副反應；藉由例如以高於常溫80 °C 溫進行洗淨，亦可望提昇洗淨性能。 本發明之洗淨液可對多種材料及形狀的被洗淨物 。被洗淨物可提及的有，例如聚矽氧、玻璃、陶瓷。 明之洗淨液可適用之被洗淨物的表面材料無特別限制 提及的有，例如單晶矽、多晶矽、非晶矽、熱矽氧化 無摻雜矽酸鹽玻璃膜、磷摻雜矽酸鹽玻璃膜、硼摻雜 鹽玻璃膜、磷硼摻雜矽酸鹽玻璃膜、TEOS膜、電漿 氧化膜、氮化矽膜、碳化矽膜、碳氧化矽膜、或碳氧 氮化膜等。另外，亦可適用於玻璃、石英、水晶、陶 6此等可爲單獨構成，亦可爲具有2種以上之分布經 化者，或經積層者。 本發明之洗淨液亦可適用於經硏磨步驟而平坦化 洗淨物。被洗淨物表面的硏磨方法無特別限制，可採 往周知的多種方法。硏磨方法係依據該被洗淨物的形 目的所需之硏磨精度適當選擇。具體而言，可提及的 例如機械硏磨或化學機械硏磨（C Μ P)等，但本發明之 液適用於使用氧化姉硏磨漿之化學機械硏磨（CMP)。 鈽硏磨獎係作爲硏磨粒之氧化姉經分散於溶液中者。 使用本發明之洗淨液之洗淨方法可採用多種濕式 法。可提及的有，例如將被洗淨物浸漬於已塡充至洗 之洗淨液中之浸漬處理方法。再者，可提及的有，藉 洗淨液吐出、噴附於旋轉中之矽晶圓等被洗淨物上進 淨處理之單晶圓處理方法等。再者，上述浸漬處理方 之高 使用 本發 ，可 膜、 矽酸 C VD 化矽 瓷等 圖案 之被 用以 狀或 有， 洗淨 氧化 洗淨 淨槽 由使 行洗 法中 -12- 201235464 ，亦可採用同時將超音波施加於洗淨液中進行 可進一步適用噴射洗淨液的同時藉由刷子洗淨, 。再者，洗淨亦可進行複數次。此時，亦可於: 理中使用不同組成或濃度之洗淨液。 洗淨時間無特殊限制，可根據附著於被洗; 铈的污染程度等適當設定。通常以1 〇分鐘以 分鐘以下較佳。洗淨時間超過10分鐘時，有] 表面被蝕刻造成表面粗糙度增大之情形。 再者，本發明之洗淨方法中，於上述洗淨丨 可適當地根據需要進行藉由超純水等清洗劑之 藉此，可防止洗淨液殘留於被洗淨物的表面。 [實施例] 以下以本發明適當的實施例爲例詳細說明。 例中所記載之材料或摻合量等，若無特別限制5 非將此發明的範圍僅限於該等之意，而是僅單斜 (洗淨液之製作方法） 有關各實施例或比較例之洗淨液，係將以下 料擇一適當摻合製作而成。實施例中所使用之鹽 下述所示之原材料之構成鹽之酸及鹽基，藉由使 反應而得。即，將（1)50重量％高純度氫氟 Chemifa股份有限公司製）、（2)EL等級，36重 方法。亦 刷洗方法 個洗淨處 物之氧化 :爲佳，1 洗淨物的 理後，亦 洗步驟。 但此實施 記載，並 爲說明例 所示原材 係將選自 該等進行 酸（S t e 11 a 量％鹽酸（ -13- 201235464 三菱化學股份有限公司製）、（3 ) E L等級，6 9重量％硝酸（ 三菱化學股份有限公司製）、（4) E L等級，9 7重量％硫酸（ 三菱化學股份有限公司製）' (5)EL等級，28重量％氨水（ 林純藥工業股份有限公司製）、（6)氫氧化四甲銨（商品名稱 :Tokuso SD-25 ’ TOKUYAMA股份有限公司製）擇一以指 定的混合比率摻合製作而成》 各實施例中使用界面活性劑時，將下述所示原材料擇 一適當摻合。即，將（1)聚氧乙烯烷基醚（非離子型界面活 性劑）、（2)庚胺（陽離子型界面活性劑）、（3)庚酸（非離子型 界面活性劑）擇一以指定濃度添加。 (被洗淨物表面之殘渣殘留狀態之測量方法） 關於被洗淨物表面之氧化鈽的固體物質之殘渣狀態， 係使用TREX6 10-T(Technos股份有限公司製）進行測量。 即，於使用洗淨液之洗淨處理前後進行測量，確認使用洗 淨液之洗淨效果。 (實施例1〜13) 如同表1所示，藉由將濃度爲〇. 001 ~5重量。/。之氟化 氫作爲成分（a)、濃度爲1〜20重量％之硫酸銨作爲成分（b) 、及水作爲成分（c)予以混合製作成洗淨液。 (實施例14〜17) 如同表1所示，藉由將濃度爲0.0 1〜0 ·1重量％之氣化 -14- 201235464 氫作爲成分（a)、濃度爲1〜1 〇重量％之硫酸四甲銨作爲成 分（b)、及水作爲成分（c)予以混合製作成洗淨液。 (實施例18) 如同表1所示，藉由將濃度爲0.1重量％之氟化氫作 爲成分（a)、濃度爲5重量％之硫酸銨、濃度爲5重量％之 氯化銨作爲成分（b )、及水作爲成分（c)予以混合製作成洗 淨液。 (比較例1) 如同表1所示，製作硫酸銨濃度爲20重量％之水溶 液。 (比較例2) 如同表1所示，製作氟化銨濃度爲20重量。/。之水溶 液。 (比較例3) 如同表1所示，藉由將濃度爲0.5重量％之氟化氫作 爲成分（a)、濃度爲2 0重量％之氣化錢作爲成分（b)、及水 作爲成分（c)予以混合製作成洗淨液。 (比較例4) 如同表1所示’製作氟化氫濃度爲5重量％之水溶液 -15- 201235464 其次’對已於表面形成5000A I 2 0 0mm之矽基板，使用氧化鈽作爲硏 硏磨’以此作爲被洗淨物使用。此被洗 鈽殘留狀態之測量確認約當1 X 1 〇 12原 殘渣成分。 接著，將上述洗淨液塡充至容積爲 ’將洗淨液溫度調節至2 5 °C使洗淨液 使上述被洗淨物固定於PFA樹脂製之 ，於上述洗淨液槽中浸漬3 0秒。浸漬 板固定構件自洗淨液槽吊起，再浸漬於 90L之超純水清洗槽中，清洗附著於被 液。之後，使被洗淨物乾燥，再次進行 。去除性能之良否以處理後之铈成分量 估裝置的檢測下限値8.5 xlO9原子/cm2 低至8.5xl09原子/cm2時爲不良。將根 結果揭示於下述表1。 匕TEOS膜之直徑 磨粒進行化學機械 淨物中，藉由上述 子/cm2之氧化铈爲 90L之洗淨液槽中 溫度安定。此時， 矽基板固定構件上 後，將其連同矽基 另行準備之容積爲 洗淨物表面之洗淨 铈殘留狀態之測量 降低至殘留狀態評 以下時爲良，未降 據此之洗淨性評估 -16- 201235464 [表i] 成分⑻ 成分(b) 成分(C) 編號 HF 種類 [重量％] 水 洗淨性 f雷量％] [重量％] 實施例1 0.001 硫酸銨 10 89.999 良 實施例2 0.01 硫酸銨 1 98.99 良 實施例3 0.01 硫酸錢 10 89.99 良 實施例4 0.01 硫酸銨 20 79.99 良 實施例5 0.1 硫酸銨 1 98.9 良 實施例6 0.1 硫酸錢 10 89.9 良 實施例7 0.1 硫酸銨 20 79.9 良 實施例8 1 硫酸銨 1 98 良 實施例9 1 硫酸銨 10 89 良 實施例10 1 硫酸錢 20 79 良 實施例11 5 硫酸銨 1 94 良 實施例12 5 硫酸銨 10 85 良 實施例13 5 硫酸銨 20 75 良 實施例14 0.01 硫酸四甲銨 5 94.99 良 實施例15 0.1 硫酸四甲銨 1 98.9 良 實施例16 0.1 硫酸四甲銨 5 94.9 良 實施例17 0.1 硫酸四甲銨 10 89.9 良 實施例18 0.1 硫酸銨 5 89.9 良 氯化銨 5 比較例1 0 硫酸銨 20 80 不良 比較例2 0 氟化銨 20 80 不良 比較例3 0.5 氟化銨 20 79.5 不良 比較例4 5 ΛπΤ. 挑 0 95 不良 由表1的結果得知使用實施例1〜1 8之洗淨液時，被 洗淨物表面之鈽成分降低至8.5 XI 09原子/cm2以下，具有 良好對氧化鈽之洗淨去除效果。 另™方面，得知比較例1〜4之洗淨液，姉成分未降低 -17- 201235464 至評估裝置的檢測下限値以下，對氧化鈽之洗淨去除效果 低。 (實施例19〜31) 如同表2所示除了變更洗淨液的組成及濃度之外，製 作與上述實施例1相同之各洗淨液。再進一步使用各洗淨 液進行與上述實施例1相同之洗淨處理等。該結果揭示於 下述表2。 (比較例5) 如同表2所示除了變更洗淨液的組成及濃度之外，製 作與上述實施例1相同之各洗淨液。再進一步使用各洗淨 液進行與上述實施例1相同之洗淨處理等。該結果揭示於 下述表2。 -18- 201235464 [表2] 成分(a) 成分⑼ 成分⑷ 編號 HF 種類 [重量％] 水 洗淨性 [重量％] [重量％] 實施例19 0.001 氯化銨 10 89.999 良 實施例20 0.01 氯化錢 1 98.99 良 實施例21 0.01 氯化錢 10 89.99 良 實施例22 0.01 氯化銨 20 79.99 良 實施例23 0.1 氯化錢 1 98.9 良 實施例24 0.1 氯化錢 10 89.9 良 實施例25 0.1 氯化錢 20 79.9 良 實施例26 1 氯化錢 1 98 良 實施例27 1 氯化銨 10 89 良 實施例28 1 氯化錢 20 79 良 實施例29 5 氯化錢 1 94 良 實施例30 5 氯化銨 10 85 良 實施例31 5 氯化銨 20 75 良 比較例5 0 氯化錢 20 80 不良 由表2的結果得知使用實施例1 9〜3 1之洗淨液時，被 洗淨物表面之鈽成分降低至8.5 X 1 09原子/cm2以下，具有 良好對氧化鈽之洗淨去除效果。 另一方面，得知比較例5之洗淨液，铈成分未降低至 評估裝置的檢測下限値以下，對氧化铈之洗淨去除效果低 (實施例32〜44) 如同表3所示除了變更洗淨液的組成及濃度之外，製 作與上述實施例1相同之各洗淨液。再進一步使用各洗淨 -19- 201235464 液進行與上述實施例1相同之洗淨處理等。該結果揭示於 下述表3。 (比較例6) 如同表3所示除了變更洗淨液的組成及濃度之外，製 作與上述實施例1相同之各洗淨液。再進一步使用各洗淨 液進行與上述實施例1相同之洗淨處理等。該結果揭示於 下述表3。 [表3] 編號 實施例32 成分⑻ 成分(b) 成分(c) 洗淨性 HF 種類 mm.%] 水 [重量％] [重量％] 0.001 硝酸銨 10 89.999 良 實施例33 0.01 硝酸銨 1 98.99 良 實施例34 0.01 硝酸銨 10 89.99 良 實施例35 0.01 硝酸銨 20 79.99 良 實施例36 0.1 硝酸銨 1 98.9 良 實施例37 0.1 硝酸銨 10 89.9 良 實施例38 0.1 硝酸銨 20 79.9 良 實施例39 1 硝酸銨 1 98 良 實施例40 1 硝酸銨 10 89 良 眚施例41 1 硝酸銨 20 79 良 實施例42 5 硝酸銨 1 94 良 實施例43 5 硝酸銨 10 85 良 實施例44 5 硝酸銨 20 75 良 比較例6 0 硝酸銨 20 80 不良 由表3的結果得知使用實施例32〜44之洗淨液時，被 -20- 201235464 洗淨物表面之鈽成分降低至8.5 χΙΟ9原子/cm2以下，具有 良好對氧化鈽之洗淨去除效果。 另一方面，得知比較例6之洗淨液，鈽成分未降低至 評估裝置的檢測下限値以下，對氧化铈之洗淨去除效果低 (實施例45~47) 如同表4所示，藉由將濃度爲0 · 1重量％之氟化氫作 爲成分（a)、濃度爲1 0重量％之硫酸銨作爲成分（b)、水作 爲成分（c)，再進一步將非離子型、陽離子型、或陰離子 型之界面活性劑予以混合製作成洗淨液。之後，進行與上 述實施例1相同之使m各洗淨液之洗淨處理等。該結果揭 示於下述表4。 [表4] 編號 成分⑷ 成分(b) 成分(C) 界面活， 生劑 洗淨性 HF 種類 [重量％] 水 種類 [ppm] [重量％] mm.%] 實施例45 0.1 硫酸銨 10 89.9 非離子型 100 良 實施例46 0.1 硫酸銨 10 89.9 陽離子型 100 良 實施例47 0.1 硫酸銨 10 89.9 陰離子型 100 良 由表4的結果得知使用本實施例45~47之洗淨液時， 被洗淨物表面之铈成分降低至8·5χ1〇9原子/cm2以下，具 有良好對氧化姉之洗淨去除效果。 -21 - 201235464 (實施例48〜59) 如同表5所示，藉由將濃度爲0.1〜5重量％之氟化氫 作爲成分（a)、濃度爲5重量％之硫酸銨、氯化銨、硝酸銨 、或硫酸四甲銨作爲成分（b)、及水作爲成分（c)予以混合 製作成洗淨液。 (比較例7) 如同表5所示，製作硫酸銨濃度爲5重量％之水溶液 (比較例8) 如同表5所示，製作氟化銨濃度爲20重量％之水溶 液。 (比較例9 ) 如同表5所示，藉由將濃度爲0.5重量％之氟化氫作 爲成分（a)、濃度爲20重量％之氟化銨作爲成分（b)、及水 作爲成分（c)予以混合製作成洗淨液。 (比較例1 0) 如同表5所示，製作氟化氫濃度爲5重量％之水溶液 〇 其次，對已於表面形成1 000A之無摻雜多晶矽膜之 直徑200mm之矽基板，使用氧化鈽作爲硏磨粒進行化學 -22- 201235464 機械硏磨，以此作爲被洗淨物使用。此被洗淨物中，藉由 下述殘渣殘留狀態之測量確認約當lxlO12原子/cm2之氧 化铈爲殘渣成分。 接著，進行與上述實施例1相同之使用各洗淨液之洗 淨處理等。該結果揭示於下述表5。 [表5] 編號 成分⑻ 成分(b) 成分⑷ 多晶矽膜上之洗淨性 HF 種類 [重量％] 水 [重量％] rma-%1 實施例48 0.1 硫酸銨 5 94.9 良 實施例49 1 硫酸錢 5 94 良 實施例50 5 硫酸銨 5 90 良 實施例51 0.1 氯化銨 5 94.9 良 實施例52 1 氯化銨 5 94 良 實施例53 5 氯化鞍 5 90 良 實施例54 0.1 硝酸銨 5 94.9 良 實施例55 1 硝酸銨 5 94 良 實施例56 5 硝酸銨 5 90 良 實施例57 0.1 硫酸四甲銨 5 94.9 良 實施例58 1 硫酸四甲銨 5 94 良 實施例59 5 硫酸四甲銨 5 90 良 比較例7 0 硫酸銨 5 95 不良 比較例8 0 氟化銨 20 80 不良 比較例9 0.5 氟化銨 20 79.5 不良 比較例10 5 無 0 95 不良 由表5的結果得知使用實施例48~59之洗淨液時’被 洗淨物表面之鈽成分降低至8.5 X 109原子/cm2以下’具有 良好對氧化鈽之洗淨去除效果° -23- 201235464 另一方面，得知比較例7~1〇之洗淨液，铈成分未降 低至評估裝置的檢測下限値以下，對氧化鈽之洗淨去除效 果低。 (實施例60〜71) 如同表6所示，藉由將濃度爲〇.1〜5重量％之氟化氫 作爲成分（a)、濃度爲5重量％之硫酸銨、氯化銨、硝酸銨 、或硫酸四甲銨作爲成分（b)、及水作爲成分（c)予以混合 製作成洗淨液。 (比較例1 1) 如同表6所示，製作硫酸銨濃度爲5重量％之水溶液 (比較例12) 如同表6所示，製作氟化銨濃度爲20重量％之水溶 液。 (比較例13) 如同表6所示，藉由將濃度爲〇.5重量％之氟化氫作 爲成分（a)、濃度爲20重量％之氟化銨作爲成分（b)、及水 作爲成分（c)予以混合製作成洗淨液。 (比較例14) -24- 201235464 如同表6所示’製作氟化氫濃度爲5重量％之水溶液 〇 其次’對已於表面形成ιοοοΑ之氮化矽膜之直徑 200mm之矽基板，使用氧化铈作爲硏磨粒進行化學機械 硏磨，以此作爲被洗淨物使用。此被洗淨物中，藉由上述 鈽殘渣殘留狀態之測量確認約當1 X 1 〇 12原子/ c m2之氧化 鈽爲殘渣成分。 接著，進行與上述實施例1相同之使用各洗淨液之洗 淨處理等。該結果揭示於下述表6。 [表6] 編號 成分⑻ 成分(b) 成分(C) 氮化矽膜上之洗淨性 HF 種類 [重量％] 水 [重量％] [重量％] 實施例60 0.1 硫酸錢 5 94.9 良 實施例61 1 硫酸錶 5 94 良 實施例62 5 硫酸銨 5 90 良 實施例63 0.1 氯化銨 5 94.9 良 實施例64 1 氯化銨 5 94 良 實施例65 5 氯化銨 5 90 良 實施例66 0.1 硝酸銨 5 94.9 良 實施例67 1 硝酸銨 5 94 良 實施例68 5 硝酸銨 5 90 良 實施例69 0.1 硫酸四甲銨 5 94.9 良 實施例70 1 硫酸四甲銨 5 94 良 實施例71 5 硫酸四甲銨 5 90 良 比較例11 0 硫酸銨 5 95 不良 比較例12 0 氟化銨 20 80 不良 比較例13 0.5 氟化錢 20 79.5 不良 比較例14 5 Μ Μ、、 0 95 不良 -25- 201235464 由表6的結果得知使用實施例60〜71之洗淨液時，被 洗淨物表面之铈成分降低至8·5χ109原子/ cm2以下，具有 良好對氧化鈽之洗淨去除效果。 另一方面，得知比較例11〜14之洗淨液，姉成分未降 低至評估裝置的檢測下限値以下，對氧化鈽之洗淨去除效 果低。 (實施例72〜74) 如同表7所示，藉由將濃度爲0.01〜0.5重量％之氟化 氣作爲成分（a)、濃度爲10重量％之硫酸錢作爲成分（b)、 及水作爲成分（〇予以混合製作成洗淨液。 (比較例1 5〜1 7) 如同表7所示，藉由將濃度爲〇. 〇 1〜〇 . 5重量％之氟化 氫作爲成分（a)、濃度爲10重量％之硫酸作爲成分（b)、及 水作爲成分（c)予以混合製作成洗淨液。 (比較例1 8) 如同表7所示，藉由將濃度爲0. 〇 1重量％之氟化氫作 爲成分（a)、濃度爲1〇重量》/。之硫酸及濃度爲〇」重量％之 抗壞血酸作爲成分（b)、及水作爲成分（c)予以混合製作成 洗淨液。 其次’各自準備已於表面形成2000A之鈦膜及5000A 之銘膜之直徑200mm之矽基板，以此作爲被洗淨物使用 -26- 201235464 接著，將上述洗淨液塡充至容積爲90L之洗淨液槽中 ，將洗淨液溫度調節至25 °C使洗淨液溫度安定。此時， 使上述被洗淨物固定於PFA樹脂製之矽基板固定構件上 ，對上述洗淨液，於表7所示之指定時間中，將附有鈦膜 及鋁膜之矽基板予以浸漬。浸漬後，將其連同矽基板固定 構件自洗淨液槽吊起，再浸漬於另行準備之容積爲90L之 超純水清洗槽中，清洗附著於被洗淨物表面之洗淨液。之 後，使被洗淨物乾燥，使用4探針型表面電阻測量儀（共 和理硏公司製，K705-RS)測量表面電阻値。該測量結果揭 示於下述表7。 m η 編號 成分⑻ 成分〇3) 成分⑹ pH 處理 時間 鈦膜表 面電阻 鋁膜表面 電阻 HF 種類 [軍暈％] 水 [重量〇/〇] [-1 [分鐘] ΓΩ/αΙ [ηιΩ/α! 無處理 0 6.9 60 實施例72 0.01 硫酸銨 10 90.0 2.8 60.0 7.1 97 實施例73 0.1 1 硫酸銨 10 89.9 2.5 3.0 7.0 110 實施例74 0.5 硫酸銨 10 89.5 2.0 0.75 7.0 130 比較例15 0.01 硫酸 10 90.0 <1 60 25 183 比較例16 0.1 硫酸 10 89.9 <1 3 154 236 比較例17 0.5 硫酸 10 89.5 <1 0.75 219 255 比較例18 0.01 硫酸 10 88.9 <1 60 18 208 抗壞血酸 0.1 由表7的結果得知使用實施例72〜74之洗淨液時，被 洗淨物表面之鈦膜及鋁膜的表面電阻値上昇幅度較比較例 -27- 201235464 1 5〜1 7小，對鈦膜及鋁膜之影響小。如此，本發明之洗淨 液不僅可將氧化姉洗淨去除，亦較比較例的洗淨液可抑制 金屬膜電阻値之增加。 另一方面，得知使用比較例1 8之洗淨液時，鈦膜及 鋁膜的表面電阻値大幅增加，即便可將氧化铈洗淨去除， 亦將使金屬膜的電阻値增加。 -28-201235464 VI. Description of the Invention: [Technical Field] The present invention relates to a washing liquid to which cerium oxide has been attached, which can be washed and removed, and washed with the cleaning liquid. method. [Prior Art] In order to achieve high performance of large integrated circuits (ULSI), the miniaturization of circuit design continues to progress. In order to form a very fine circuit structure that is micronized to the nanometer level, many manufacturing steps require new manufacturing techniques that have not yet been applied. In particular, the most important step of forming a fine structure on a semiconductor raft has an exposure and development step using an optical technique. In order to produce this fine structure, the same and uniform focusing on the surface of the semiconductor substrate is closely related to the flatness of the surface of the substrate. That is, when the flatness of the surface of the substrate is not good, a focused portion and an unfocused portion are formed on the surface of the substrate, and the unfocused portion cannot form a desired fine structure, resulting in a drastic decrease in productivity. Further, as the progress of miniaturization, the allowable range of flatness is reduced, and the flattening requirement of the substrate surface is further improved. Furthermore, in addition to the requirements for flattening, there is also a need to shorten the step time for the purpose of improving production efficiency. Therefore, there is a need for a technique that speeds up the steps in addition to the processing precision of fine processing. In this technical background, chemical mechanical honing (C Μ P) is generally performed as a technique for ensuring flatness. The CMP system is used to honing (flattening) the surface of the semiconductor substrate using a honing pad while supplying a honing agent (rubber slurry) containing granulated honing particles. 201235464 In the above CMP, cerium oxide refining is widely used as a honing agent, but cerium oxide is also used for refining. As in the case of cerium dioxide refining, it is necessary to remove the residue remaining on the surface of the substrate. Washing steps. For the detergent used in the washing step, for example, the following proposals are made. Patent Document 1 discloses a cleaning chemical solution containing three components of an acid, a reducing agent, and a fluoride ion. Patent Document 2 discloses a cleaning liquid composed of hydrogen fluoride and sulfuric acid or nitric acid or phosphoric acid. However, even if the conventional cleaning liquid can remove the residue of cerium oxide, since acid is the main component, there is a problem that various metal materials are easily corroded. For example, when the metal film on the semiconductor substrate is dissolved by corrosion, the film thickness of the metal film is reduced, and the surface resistance 金属 of the metal film is increased. As a result, the resistance of the wiring on the integrated circuit becomes large, and the increase in power consumption is not preferable. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] JP-A-2000-140778 [Patent Document 2] JP-A-2000-140778 [Summary of the Invention] [Problems to be Solved by the Invention] The object of the present invention is to provide a cleaning solution for depositing cerium oxide on a surface, which can dissolve the cerium oxide into cerium ions to remove it, and which is not easy to corrode various metal materials, and use the same Washing method of washing liquid -6 - 201235464 [Means for Solving the Problem] In order to solve the above conventional problems, the inventors of the present invention have studied the cleaning liquid and the washing method using the same. As a result, it has been found that by using a cleaning liquid containing hydrogen fluoride and a specific ammonium salt, the cerium oxide remaining on the surface of the object to be washed can be efficiently washed and removed, and the present invention has been completed. That is, the present invention relates to a cleaning liquid which is a cleaning liquid which removes cerium oxide remaining on the surface of the object to be washed, and is characterized in that it contains (1) hydrogen fluoride, and (2) at least one selected from the group consisting of chlorination. An ammonium salt of the group consisting of ammonium, ammonium nitrate, ammonium sulfate, tetramethylammonium chloride, tetramethylammonium nitrate, and tetramethylammonium sulfate. By containing hydrogen fluoride in the cleaning liquid, cerium oxide can be dissolved into cerium ions. However, the dissolved cerium ions adhere to the surface of the object to be washed again as impurities, and as a result, it is difficult to remove the cerium component. The present inventors have found that by dissolving hydrogen fluoride and a specific hinge salt in the cleaning liquid, the dissolved ammonium ions can be stably dissolved in the cleaning liquid in a dissolved state, and can be efficiently removed from the surface of the object to be washed. Further, the cleaning liquid of the present invention is not limited to an acid such as sulfuric acid, nitric acid or phosphoric acid as a main component of the cleaning liquid of the present invention, so that corrosion of various metal materials can be suppressed. Further, the cerium ion means Ce3+, Ce4+, these hydrates, or the like. The concentration of hydrogen fluoride in the cleaning liquid is preferably 0.001 to 5% by weight. When the concentration of hydrogen fluoride is less than 0.001% by weight, the solubility of cerium oxide tends to decrease. On the other hand, when it exceeds 5% by weight, the object to be washed is corroded by uranium engraving or 201235464, and the surface roughness of the object to be cleaned by honing tends to increase. In addition, after the "cleaning treatment", the hydrogen fluoride in the washing liquid is harmless, and the required cost and time will increase. The concentration of the above ammonium salt in the washing liquid is preferably ο.1-20% by weight. . When the concentration of the above ammonium salt is less than 0.1% by weight, it is difficult to stabilize the dissolved ammonium ion in the cleaning state in a dissolved state. It is difficult to wash and remove the cerium component from the surface of the object to be washed. On the other hand, when it exceeds 20% by weight, the solubility of cerium oxide tends to decrease, and it is difficult to maintain the properties of the solution due to the occurrence of precipitates, which tends to cause defects during cleaning. The above cleaning solution preferably contains a surfactant. By including the surfactant in the cleaning liquid, the surface tension of the cleaning liquid is lowered, and the wettability to the surface of the object to be washed can be improved. Thereby, the washing and removing effect can be made uniform in a wide range of the surface of the object to be washed, so that productivity can be expected to be improved. Furthermore, the present invention relates to a cleaning method which is a method for washing a cerium oxide by dissolving cerium oxide into cerium ions by contacting the cleaning liquid with the surface of the cerium-attached rinsing object. Characterized by the use of the above-mentioned cleaning liquid containing (1) hydrogen fluoride, and (2) at least one selected from the group consisting of ammonium chloride, ammonium nitrate, ammonium sulfate, tetramethylammonium chloride, tetramethylammonium nitrate, and tetramethylammonium sulfate. A group of ammonium salt washes. In the above cleaning method, the concentration of hydrogen fluoride in the cleaning liquid is preferably 0.001 to 5% by weight, and the concentration of the ammonium salt is preferably 0. 1 to 2% by weight. The reason is as above. -8 - 201235464 Further, in the above washing method, the cleaning liquid preferably contains a surfactant. The reason is as above. Further, the above cleaning method is applied to a case where the object to be cleaned is a semiconductor substrate, a glass substrate, a ceramic substrate, a quartz substrate, or a crystal substrate. [Effect of the Invention] According to the present invention, the cerium oxide remaining on the surface of the object to be washed which is honed using the cerium oxide-containing honing agent can be efficiently removed and has an advantage that various metal materials are not easily corroded. Therefore, in the manufacturing process of a semiconductor device, for example, the residue of cerium oxide can be efficiently removed from the honed semiconductor substrate, and the productivity of the semiconductor device can be improved. Further, since the corrosion of the metal material on the semiconductor substrate and the metal material constituting the semiconductor device can be suppressed, the performance of the semiconductor device can be improved. [Embodiment] An embodiment of the cleaning liquid according to the present invention will be described below. The cleaning solution of the present invention comprises (1) hydrogen fluoride and (2) at least one selected from the group consisting of ammonium chloride, ammonium nitrate, ammonium sulfate, tetramethylammonium chloride, tetramethylammonium nitrate, and tetramethylammonium sulfate. The group of ammonium salts is suitable for use in the removal of cerium oxide remaining on the surface of the honed cleaned material by using a honing agent containing cerium oxide as the honing granule. In particular, when it is suitable to wash and remove cerium oxide remaining on the surface of the chemical mechanical honing (CMP) by using cerium oxide refining, the concentration of hydrogen fluoride in the cleaning liquid is preferably 0.001 to 5% by weight. '-9- 201235464 0.001 to 2% by weight is preferred. By lowering the concentration of hydrogen fluoride, the cerium oxide can be efficiently removed by washing, and the etching and corrosion of the material on the surface of the object to be washed can be suppressed. The concentration of the above ammonium salt in the cleaning liquid is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably 0 to 1 to 5% by weight. By reducing the concentration of ammonium salts, resources can be saved and costs can be saved during the preparation phase of the liquid medicine. Specifically, the stock solution of the concentrated component concentration can be prepared, and the stock solution is diluted with water or the like to the above-mentioned concentration before the washing treatment. Thereby, the resources or costs substantially related to the manufacture of the cleaning liquid or the charging of the shipping container, and the resources or costs associated with the transportation of the cleaning liquid that has been charged to the shipping container are reduced, in other words, can be improved Productivity. In the cleaning liquid of the present invention, the components other than the above are preferably water-based, but may contain components other than water. Mention may be made, for example, as an interface active agent, a chelating agent, a pH 値 adjusting agent, an organic solvent or the like. However, when using this, it is necessary to consider the resistance to the organic components of the cleaning device, the cost at the time of disposal, and the danger during use. The cleaning solution of the present invention preferably contains a surfactant. The surfactant is not particularly limited, and examples thereof include an anionic surfactant such as an aliphatic carboxylic acid or a salt thereof, a nonionic surfactant such as a polyethylene glycol alkyl ether, an aliphatic amine or a salt thereof, and the like. Cationic surfactants and the like. The amount of the surfactant to be added is preferably in the range of 0.001 to 0.1% by weight, more preferably in the range of 0.003 to 0.05% by weight. By adding a surfactant, it is possible to suppress the roughness of the surface of the object to be washed which has been subjected to the cleaning treatment. The wettability of the washed matter is further improved, and the uniformity of the washing effect in the in-plane -10- 201235464 is expected to be achieved. However, when the amount added is less than 0.001% by weight, the surface tension of the cleaning liquid cannot be sufficiently lowered. Therefore, the effect of improving the wettability is insufficient. Further, when the amount added exceeds 〇. 1% by weight, not only the corresponding effect cannot be obtained, but also the defoaming property is deteriorated, and the foam adheres to the surface of the object to be washed, resulting in uneven washing. The purity and the cleanliness of the above-mentioned cleaning liquid are preferably set in consideration of the problem of contamination of the washed matter subjected to the washing treatment and the production 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 1 ppb or less. The cleaning solution of the present invention can be prepared by mixing hydrogen fluoride, the above ammonium salt, and other optional components in an arbitrary order. Alternatively, a compound obtained by mixing the above various components may be used as a raw material, and a washing liquid having the above components and concentrations may be finally prepared. Specifically, the washing liquid of the present invention can be prepared by mixing hydrogen fluoride, sulfuric acid, ammonia, and water. Namely, ammonium sulfate is formed by neutralizing sulfuric acid with ammonia. Further, the washing liquid of the invention can be prepared by mixing, for example, ammonium fluoride, sulfuric acid and ammonia. The cleaning liquid of the present invention may be formed in the washing stage corresponding to the use stage, and there is no limitation on the manner of the preparation stage. For example, it is also possible to prepare a concentrated stock solution of the washing liquid up to the place of use, and dilute and prepare the washing liquid of the invention before use. Alternatively, for example, the components may be separately prepared and mixed and prepared for use in the cleaning solution of the invention before use. The use temperature of the cleaning liquid of the present invention is not limited at all. In practice, it is preferable to use it at a normal temperature in a useful temperature region. Further, depending on the washing conditions, for example, washing at a temperature lower than normal temperature of 10 ° C can suppress side reactions other than washing by -11 - 201235464; for example, at a temperature higher than normal temperature of 80 ° C Washing, but also hope to improve the cleaning performance. The cleaning solution of the present invention can be used to wash a variety of materials and shapes. Mention may be made, for example, of polyoxyn, glass, ceramics. The surface material of the cleaned liquid which can be applied is not particularly limited, such as single crystal germanium, polycrystalline germanium, amorphous germanium, hot tantalum oxide undoped tantalate glass film, phosphorus doped tannic acid. Salt glass film, boron doped salt glass film, phosphorous boron doped silicate glass film, TEOS film, plasma oxide film, tantalum nitride film, tantalum carbide film, tantalum carbon oxide film, carbon oxynitride film, etc. . Further, it may be applied to glass, quartz, crystal, or ceramics. 6 or the like may be used alone or in combination of two or more types, or laminated. The cleaning solution of the present invention can also be applied to the scouring step to planarize the laundry. The honing method of the surface of the object to be washed is not particularly limited, and various methods known in the art can be employed. The honing method is appropriately selected in accordance with the honing precision required for the shape of the object to be washed. Specifically, for example, mechanical honing or chemical mechanical honing (C Μ P) or the like can be mentioned, but the liquid of the present invention is suitable for chemical mechanical honing (CMP) using cerium oxide refining. The honing prize is used as a cerium oxide of honing particles dispersed in a solution. A variety of wet methods can be employed for the cleaning method using the cleaning solution of the present invention. There may be mentioned, for example, an immersion treatment method in which the object to be washed is immersed in the washing liquid which has been charged to the washing. Further, there may be mentioned a single wafer processing method in which a cleaning liquid is ejected, and is ejected onto a workpiece such as a rotating wafer. In addition, the above-mentioned immersion treatment method is used in the high-grade, and the film, the citrate C VD enamel, and the like are used in the form of or the like, and the oxidative cleaning and cleaning of the groove is performed by the washing method -12-201235464 Alternatively, the ultrasonic wave may be applied to the cleaning liquid at the same time to further apply the jet cleaning liquid while being washed by a brush. Furthermore, washing can also be carried out several times. In this case, it is also possible to use a cleaning solution of different composition or concentration in the process. The washing time is not particularly limited, and may be appropriately set depending on the degree of contamination attached to the surface to be washed; It is usually preferably 1 minute or less in minutes. When the cleaning time exceeds 10 minutes, there is a case where the surface is etched to cause an increase in surface roughness. In the cleaning method of the present invention, it is possible to prevent the cleaning liquid from remaining on the surface of the object to be washed by appropriately performing a cleaning agent such as ultrapure water as needed. [Examples] Hereinafter, a preferred embodiment of the present invention will be described in detail as an example. The materials, the blending amounts, and the like described in the examples are not particularly limited. The scope of the invention is not limited to the above, but only the monoclinic (manufacturing method of the cleaning liquid). The washing liquid is prepared by appropriately mixing the following materials. Salts used in the examples The acid and the salt of the constituent salts of the raw materials shown below are obtained by a reaction. That is, (1) 50% by weight of high-purity hydrofluorination Chemifa Co., Ltd.), (2) EL grade, 36 weight method. Also, the method of scrubbing is to oxidize the cleansing material: preferably, after washing, the washing step is also carried out. However, in this embodiment, the raw material shown in the description will be selected from the above-mentioned acid (S te 11 a % hydrochloric acid (-13-201235464 manufactured by Mitsubishi Chemical Corporation), (3) EL grade, 6 9 Weight % nitric acid (Mitsubishi Chemical Co., Ltd.), (4) EL grade, 9.7 wt% sulfuric acid (manufactured by Mitsubishi Chemical Corporation)' (5) EL grade, 28% by weight ammonia water (Lin Chun Pharmaceutical Co., Ltd.) (6) tetramethylammonium hydroxide (trade name: Tokuso SD-25 'made by TOKUYAMA Co., Ltd.) is prepared by blending at a specified mixing ratio. When surfactants are used in the examples, The following materials are appropriately blended, that is, (1) polyoxyethylene alkyl ether (nonionic surfactant), (2) heptylamine (cationic surfactant), (3) heptanoic acid (Non-ionic surfactant) is added at a specified concentration. (Measurement method of residual state of residue on the surface of the object to be washed) Regarding the state of residue of solid matter of cerium oxide on the surface of the object to be washed, TREX6 10- T (Technos Co., Ltd. The measurement was performed, that is, the measurement was performed before and after the washing treatment using the cleaning liquid, and the washing effect of the cleaning liquid was confirmed. (Examples 1 to 13) As shown in Table 1, the concentration was 〇. 001. ~5 wt% of hydrogen fluoride as component (a), ammonium sulfate having a concentration of 1 to 20% by weight as component (b), and water as component (c) are mixed to prepare a cleaning solution. (Example 14~ 17) As shown in Table 1, by using gasification-14-201235464 hydrogen with a concentration of 0.01 to 0.1% by weight as component (a), tetramethylammonium sulfate having a concentration of 1 to 1% by weight as a component (b) and water were mixed as a component (c) to prepare a cleaning liquid. (Example 18) As shown in Table 1, hydrogen fluoride having a concentration of 0.1% by weight was used as the component (a) and the concentration was 5 weight. Amount of ammonium sulfate, ammonium chloride having a concentration of 5% by weight as component (b), and water as component (c) were mixed to prepare a cleaning solution. (Comparative Example 1) As shown in Table 1, ammonium sulfate concentration was prepared. It is an aqueous solution of 20% by weight. (Comparative Example 2) As shown in Table 1, a water having an ammonium fluoride concentration of 20% by weight was prepared. (Comparative Example 3) As shown in Table 1, a vaporized amount of hydrogen fluoride having a concentration of 0.5% by weight as a component (a) and a concentration of 20% by weight was used as the component (b) and water as a component ( c) The mixture was mixed to prepare a cleaning solution. (Comparative Example 4) As shown in Table 1, 'Aqueous solution having a hydrogen fluoride concentration of 5% by weight was produced -15-201235464. Next, a substrate of 5000 A I 200 mm was formed on the surface. The use of cerium oxide as a honing 'is used as a washed object. The measurement of the state of being washed is confirmed to be about 1 X 1 〇 12 original residue component. Next, the cleaning liquid is charged to a volume of 'the temperature of the cleaning liquid is adjusted to 25 ° C, and the cleaning liquid is fixed to the PFA resin by the cleaning liquid, and is immersed in the cleaning liquid tank. 0 seconds. The dipping plate fixing member is lifted from the washing liquid tank, and then immersed in a 90 L ultrapure water washing tank, and cleaned and attached to the liquid. Thereafter, the object to be washed is dried and carried out again. Whether the removal performance is good or not is determined by the lower limit of detection of the ruthenium component after treatment 値 8.5 x lO 9 atoms/cm 2 as low as 8.5 x 10 9 atoms/cm 2 . The root results are disclosed in Table 1 below. The diameter of the 匕TEOS film The abrasive grains are subjected to chemical mechanical cleaning, and the temperature in the washing liquid tank of 90 L in the above-mentioned sub-cm/cm2 is stabilized. At this time, after the substrate fixing member is placed on the substrate, the volume of the cleaning state of the surface of the cleaning material prepared separately from the substrate is reduced to the residual state, and the cleaning property is not lowered. Evaluation-16 - 201235464 [Table i] Ingredient (8) Ingredient (b) Ingredient (C) No. HF Species [% by weight] Water washing property f Thunder %] [% by weight] Example 1 0.001 Ammonium sulfate 10 89.999 Good example 2 0.01 ammonium sulfate 1 98.99 good example 3 0.01 sulfuric acid money 10 89.99 good example 4 0.01 ammonium sulfate 20 79.99 good example 5 0.1 ammonium sulfate 1 98.9 good example 6 0.1 sulfuric acid money 10 89.9 good example 7 0.1 ammonium sulfate 20 79.9 Good example 8 1 Ammonium sulfate 1 98 Good example 9 1 Ammonium sulfate 10 89 Good example 10 1 Sulfuric acid money 20 79 Good example 11 5 Ammonium sulfate 1 94 Good example 12 5 Ammonium sulfate 10 85 Good example 13 5 ammonium sulfate 20 75 good example 14 0.01 tetramethylammonium sulfate 5 94.99 good example 15 0.1 tetramethylammonium sulfate 1 98.9 good example 16 0.1 tetramethylammonium sulfate 5 94.9 good example 17 0.1 tetramethylammonium sulfate 10 89.9 Example 18 0.1 Ammonium sulfate 5 89.9 Ammonium chloride 5 Comparative Example 1 0 Ammonium sulfate 20 80 Poor Comparative Example 2 0 Ammonium fluoride 20 80 Poor Comparative Example 3 0.5 Ammonium fluoride 20 79.5 Poor Comparative Example 4 5 ΛπΤ. Pick 0 95 Defects From the results of Table 1, it was found that when the cleaning solutions of Examples 1 to 18 were used, the ruthenium content of the surface of the object to be washed was reduced to 8.5 XI 09 atoms/cm 2 or less, and the cerium oxide was washed and removed. . On the other hand, in the case of the TM, it was found that the cleaning liquid of Comparative Examples 1 to 4 did not lower the 姊 component from -17 to 201235464 to the lower limit of detection of the evaluation device, and the effect of washing and removing cerium oxide was low. (Examples 19 to 31) Each of the cleaning liquids similar to those in the above Example 1 was prepared as shown in Table 2 except that the composition and concentration of the cleaning liquid were changed. Further, the same washing treatment and the like as in the above-described Example 1 were carried out using each of the cleaning liquids. The results are disclosed in Table 2 below. (Comparative Example 5) Each of the cleaning liquids similar to those in the above Example 1 was prepared as shown in Table 2 except that the composition and concentration of the cleaning liquid were changed. Further, the same washing treatment and the like as in the above-described Example 1 were carried out using each of the cleaning liquids. The results are disclosed in Table 2 below. -18- 201235464 [Table 2] Component (a) Component (9) Component (4) No. HF Species [% by weight] Water repellency [% by weight] [% by weight] Example 19 0.001 Ammonium chloride 10 89.999 Good example 20 0.01 Chlorine Money 1 98.99 Good example 21 0.01 Chlorinated money 10 89.99 Good example 22 0.01 Ammonium chloride 20 79.99 Good example 23 0.1 Chlorinated money 1 98.9 Good example 24 0.1 Chlorinated money 10 89.9 Good example 25 0.1 Chlorine Money 20 79.9 Good example 26 1 Chlorinated money 1 98 Good example 27 1 Ammonium chloride 10 89 Good example 28 1 Chlorinated money 20 79 Good example 29 5 Chlorinated money 1 94 Good example 30 5 Chlorine Ammonium 10 85 Good Example 31 5 Ammonium chloride 20 75 Good Comparative Example 5 0 Chlorinated money 20 80 Poor From the results of Table 2, it was found that the washed matter was used when the cleaning solution of Example 1 9 to 3 1 was used. The surface composition of the crucible is reduced to 8.5 X 1 09 atoms/cm 2 or less, and has a good cleaning and removing effect on cerium oxide. On the other hand, when the cleaning liquid of Comparative Example 5 was found, the bismuth component was not lowered to the lower limit of detection of the evaluation device, and the effect of washing and removing cerium oxide was low (Examples 32 to 44), except as shown in Table 3. In addition to the composition and concentration of the cleaning liquid, the same cleaning liquid as in the above Example 1 was prepared. Further, the same washing treatment and the like as in the above Example 1 were carried out using each of the washing -19-201235464 liquid. The results are disclosed in Table 3 below. (Comparative Example 6) Each of the cleaning liquids similar to those in the above Example 1 was prepared as shown in Table 3 except that the composition and concentration of the cleaning liquid were changed. Further, the same washing treatment and the like as in the above-described Example 1 were carried out using each of the cleaning liquids. The results are disclosed in Table 3 below. [Table 3] No. Example 32 Component (8) Component (b) Component (c) Detergency HF Species mm.%] Water [% by weight] [% by weight] 0.001 Ammonium nitrate 10 89.999 Good example 33 0.01 Ammonium nitrate 1 98.99 Good example 34 0.01 Ammonium nitrate 10 89.99 Good example 35 0.01 Ammonium nitrate 20 79.99 Good example 36 0.1 Ammonium nitrate 1 98.9 Good example 37 0.1 Ammonium nitrate 10 89.9 Good example 38 0.1 Ammonium nitrate 20 79.9 Good example 39 1 Ammonium nitrate 1 98 Good example 40 1 Ammonium nitrate 10 89 Good 眚 Example 41 1 Ammonium nitrate 20 79 Good example 42 5 Ammonium nitrate 1 94 Good example 43 5 Ammonium nitrate 10 85 Good example 44 5 Ammonium nitrate 20 75 Comparative Example 6 0 Ammonium Nitrate 20 80 Defect According to the results of Table 3, when the cleaning liquids of Examples 32 to 44 were used, the surface component of the surface of the -20-201235464 laundry was reduced to 8.5 χΙΟ 9 atoms/cm 2 or less. It has a good cleaning and removing effect on cerium oxide. On the other hand, when the cleaning liquid of Comparative Example 6 was found, the bismuth component was not lowered below the detection lower limit 评估 of the evaluation device, and the effect of washing and removing cerium oxide was low (Examples 45 to 47) as shown in Table 4, The hydrogen fluoride having a concentration of 0.1% by weight is used as the component (a), ammonium sulfate having a concentration of 10% by weight as the component (b), and water as the component (c), and further nonionic, cationic, or The anionic surfactant is mixed to form a cleaning solution. Thereafter, the washing treatment of the respective washing liquids of m and the like in the same manner as in the above-described Example 1 was carried out. The results are disclosed in Table 4 below. [Table 4] No. Component (4) Component (b) Component (C) Interface activity, green detergent HF type [% by weight] Water type [ppm] [% by weight] mm.%] Example 45 0.1 Ammonium sulfate 10 89.9 Nonionic 100 Good Example 46 0.1 Ammonium Sulfate 10 89.9 Cationic 100 Good Example 47 0.1 Ammonium Sulfate 10 89.9 Anionic 100 Good results from Table 4 show that when using the cleaning solutions of Examples 45 to 47, The ruthenium component on the surface of the laundry is reduced to 8·5χ1〇9 atoms/cm2 or less, and has a good cleaning and removing effect on cerium oxide. -21 - 201235464 (Examples 48 to 59) As shown in Table 5, ammonium fluoride, ammonium chloride, ammonium nitrate having a concentration of 0.1 to 5% by weight of hydrogen fluoride as the component (a) and a concentration of 5% by weight Or tetramethylammonium sulfate as a component (b) and water as a component (c) are mixed to prepare a cleaning solution. (Comparative Example 7) An aqueous solution having an ammonium sulfate concentration of 5% by weight was prepared as shown in Table 5 (Comparative Example 8). As shown in Table 5, an aqueous solution having an ammonium fluoride concentration of 20% by weight was prepared. (Comparative Example 9) As shown in Table 5, hydrogen fluoride having a concentration of 0.5% by weight was used as the component (a), ammonium fluoride having a concentration of 20% by weight as the component (b), and water as the component (c). Mix and make into a cleaning solution. (Comparative Example 1 0) As shown in Table 5, an aqueous solution having a hydrogen fluoride concentration of 5% by weight was produced, and a tantalum substrate having a diameter of 200 mm having an undoped polycrystalline tantalum film having a surface of 1 000 A was formed using yttrium oxide as a honing machine. Granules are chemically -22- 201235464 mechanical honing, which is used as a washed object. In the object to be washed, it was confirmed that cerium oxide of about 1×10 12 atoms/cm 2 was a residue component by measurement of the residual state of the residue described below. Next, the same washing treatment as that of the above-described first embodiment using the respective cleaning liquids was carried out. The results are disclosed in Table 5 below. [Table 5] No. Component (8) Component (b) Component (4) Detergency HF on polycrystalline yttrium type [% by weight] Water [% by weight] rma-%1 Example 48 0.1 Ammonium sulfate 5 94.9 Good example 49 1 Sulfuric acid money 5 94 Good example 50 5 Ammonium sulfate 5 90 Good example 51 0.1 Ammonium chloride 5 94.9 Good example 52 1 Ammonium chloride 5 94 Good example 53 5 Chlorinated saddle 5 90 Good example 54 0.1 Ammonium nitrate 5 94.9 Good Example 55 1 Ammonium Nitrate 5 94 Good Example 56 5 Ammonium Nitrate 5 90 Good Example 57 0.1 Tetramethylammonium Sulfate 5 94.9 Good Example 58 1 Tetramethylammonium Sulfate 5 94 Good Example 59 5 Tetramethylammonium Sulfate 5 90 good comparative example 7 0 ammonium sulfate 5 95 bad comparative example 8 0 ammonium fluoride 20 80 bad comparative example 9 0.5 ammonium fluoride 20 79.5 bad comparative example 10 5 no 0 95 defective from the results of Table 5 When the cleaning solution of ~59 is reduced to '8.5 X 109 atoms/cm2 below the surface of the washed object', it has a good cleaning effect on the cerium oxide. -23- 201235464 On the other hand, the comparative example 7 is known. ~1〇 washing solution, the 铈 component is not reduced to the lower limit of the evaluation device Hereinafter, the cerium oxide to remove low cleaning effect. (Examples 60 to 71) As shown in Table 6, by using hydrogen fluoride having a concentration of 0.1 to 5% by weight as the component (a), ammonium sulfate having a concentration of 5% by weight, ammonium chloride, ammonium nitrate, or Tetramethylammonium sulfate is mixed as a component (b) and water as a component (c) to prepare a cleaning solution. (Comparative Example 1 1) An aqueous solution having an ammonium sulfate concentration of 5% by weight was prepared as shown in Table 6 (Comparative Example 12). As shown in Table 6, an aqueous solution having an ammonium fluoride concentration of 20% by weight was prepared. (Comparative Example 13) As shown in Table 6, hydrogen fluoride having a concentration of 0.5% by weight was used as the component (a), ammonium fluoride having a concentration of 20% by weight as the component (b), and water as a component (c). ) is mixed to make a cleaning solution. (Comparative Example 14) -24-201235464 As shown in Table 6, 'Preparation of an aqueous solution having a hydrogen fluoride concentration of 5% by weight, and secondly, a substrate having a diameter of 200 mm which was formed on the surface of a tantalum nitride film, using yttrium oxide as a ruthenium. The abrasive grains are subjected to chemical mechanical honing to be used as a laundry. In the object to be washed, it was confirmed by measurement of the residual state of the above ruthenium residue that ruthenium oxide of about 1 X 1 〇 12 atoms/cm 2 was a residue component. Next, the same washing treatment as that of the above-described first embodiment using the respective cleaning liquids was carried out. The results are disclosed in Table 6 below. [Table 6] No. Component (8) Component (b) Component (C) Detergency HF on the tantalum nitride film [% by weight] Water [% by weight] [% by weight] Example 60 0.1 Sulfuric acid money 5 94.9 Good example 61 1 sulfuric acid table 5 94 good example 62 5 ammonium sulfate 5 90 good example 63 0.1 ammonium chloride 5 94.9 good example 64 1 ammonium chloride 5 94 good example 65 5 ammonium chloride 5 90 good example 66 0.1 Ammonium nitrate 5 94.9 Good example 67 1 Ammonium nitrate 5 94 Good example 68 5 Ammonium nitrate 5 90 Good example 69 0.1 Tetramethylammonium sulfate 5 94.9 Good example 70 1 Tetramethylammonium sulfate 5 94 Good example 71 5 Sulfuric acid Tetramethylammonium 5 90 good comparative example 11 0 ammonium sulfate 5 95 bad comparative example 12 0 ammonium fluoride 20 80 bad comparative example 13 0.5 fluorinated money 20 79.5 poor comparative example 14 5 Μ 、, 0 95 bad-25- 201235464 From the results of Table 6, it was found that when the cleaning liquids of Examples 60 to 71 were used, the ruthenium content on the surface of the object to be washed was lowered to 8.5 χ 109 atoms/cm 2 or less, and the cerium oxide was cleaned and removed. On the other hand, in the cleaning liquids of Comparative Examples 11 to 14, the bismuth component was not lowered to the lower limit of detection of the evaluation device, and the effect of washing and removing cerium oxide was low. (Examples 72 to 74) As shown in Table 7, a sulfuric acid gas having a concentration of 0.01 to 0.5% by weight as a component (a) and a sulfuric acid having a concentration of 10% by weight was used as the component (b) and water. The components (the mixture were mixed to prepare a cleaning solution. (Comparative Example 1 5 to 1 7) As shown in Table 7, hydrogen fluoride having a concentration of 〇. 〇1 to 〇. 5 wt% was used as the component (a), concentration. 10% by weight of sulfuric acid was used as the component (b), and water was added as a component (c) to prepare a cleaning solution. (Comparative Example 1 8) As shown in Table 7, the concentration was 0. 〇1% by weight The hydrogen fluoride is used as a component (a), a concentration of 1 〇 by weight of sulfuric acid, and a concentration of ascorbic acid as a component (b) and water as a component (c) to prepare a cleaning liquid. Each of the titanium film having a surface of 2000A and a film of 5000A was placed on the surface to form a substrate having a diameter of 200 mm, which was used as a material to be washed. -26-201235464 Next, the cleaning liquid was filled to a volume of 90L. In the liquid tank, the temperature of the washing liquid is adjusted to 25 ° C to stabilize the temperature of the washing liquid. The rinsing material was fixed to a ruthenium substrate fixing member made of PFA resin, and the ruthenium substrate with the titanium film and the aluminum film was immersed in the cleaning liquid for the specified time shown in Table 7. After immersion, the immersion substrate was immersed. The substrate fixing member is lifted from the cleaning liquid tank, and immersed in a separately prepared ultra-pure water washing tank having a volume of 90 L to wash the washing liquid adhering to the surface of the object to be washed. After drying, the surface resistance 値 was measured using a 4-probe surface resistance measuring instrument (K705-RS, manufactured by Kyowa Ryokan Co., Ltd.). The measurement results are shown in the following Table 7. m η No. component (8) Component 〇 3) Component (6) pH treatment Time Titanium Film Surface Resistance Aluminum Film Surface Resistance HF Type [Army%] Water [Weight 〇/〇] [-1 [Minute] ΓΩ/αΙ [ηιΩ/α! No treatment 0 6.9 60 Example 72 0.01 Ammonium sulfate 10 90.0 2.8 60.0 7.1 97 Example 73 0.1 1 Ammonium sulfate 10 89.9 2.5 3.0 7.0 110 Example 74 0.5 Ammonium sulfate 10 89.5 2.0 0.75 7.0 130 Comparative Example 15 0.01 Sulfuric acid 10 90.0 <1 60 25 183 Comparative Example 16 0.1 Sulfuric acid 10 89.9 <;1 3 154 236 Comparative Example 17 0.5 Sulfur Acid 10 89.5 <1 0.75 219 255 Comparative Example 18 0.01 Sulfuric acid 10 88.9 <1 60 18 208 Ascorbic acid 0.1 From the results of Table 7, it was found that the titanium of the surface of the object to be washed was used when the cleaning liquids of Examples 72 to 74 were used. The surface resistance of the film and the aluminum film increased by a small amount compared with the comparative example -27-201235464 1 5 to 1 7 and had little effect on the titanium film and the aluminum film. Thus, the cleaning liquid of the present invention can not only remove and remove cerium oxide, but also suppress the increase in the resistance of the metal film compared with the cleaning liquid of the comparative example. On the other hand, when the cleaning liquid of Comparative Example 18 was used, the surface resistance 钛 of the titanium film and the aluminum film was greatly increased, and even if the cerium oxide was washed and removed, the electric resistance 金属 of the metal film was increased. -28-