[0013] ＜＜洗淨液＞＞ 本發明之洗淨液為含有上述一般式(1)表示之烷醇羥胺(在本說明書，有時單簡稱為「烷醇羥胺」)、與上述一般式(2)表示之烷醇胺(在本說明書，有時單簡稱為「烷醇胺」)、溶劑以及該烷醇羥胺及該烷醇胺以外之鹼性化合物(在本說明書，有時單簡稱為「鹼性化合物」)或酸性化合物之任一種之組成物，該組成物(典型上為液狀組成物)適合作為洗淨液、防腐蝕劑。 [0014] 又，本實施態樣之洗淨液較佳為在上述一般式(1)之Ra1
與在上述一般式(2)之Rb1
為同一基，在上述一般式(1)之Ra2
與在上述一般式(2)之Rb2
為同一基。又，本實施態樣之洗淨液較佳為在上述一般式(1)之Ra1
與Ra2
為同一基，在上述一般式(2)之Rb1
與Rb2
為同一基，更佳為Ra1
、Ra2
、Rb1
及Rb2
為同一基。 [0015] 該洗淨液適合作為半導體設備、液晶顯示器(LCD)等之電子零件之洗淨液。例如，適合作為在半導體之製造步驟之光刻步驟、蝕刻步驟、化學機械性研磨(CMP)等之FEOL(Front End of Line)步驟或配線形成步驟等之BEOL(Back End of Line)步驟，或矽貫通電極(TSV)，或C4工法(Controlled Collapse Chip Connection)等之後步驟所使用之洗淨液，適合使用在於表面具有金屬之基板的洗淨。所謂於表面具有金屬之基板，係指於基板表面之至少一部分露出金屬的基板。金屬例如作為在形成半導體設備之基板的金屬配線層、插頭、其他金屬構造物所形成之金屬。作為基板，可列舉於矽晶圓等之基板上層合金屬配線層、低介電材料層、絕緣層等，形成半導體設備之基板等。又，作為基板，可為具備包含鍺等之矽化物層的基板。本實施態樣之洗淨液適合在光刻之洗淨和光刻用洗淨，可作為光刻用洗淨液使用。 [0016] 作為上述金屬，可列舉易腐蝕性金屬之鈷或其合金等。作為鈷之合金，可列舉與其他過渡元素及典型元素(例如磷、硼、矽等)中之至少1種的合金，具體而言，例示有CoWPB等之含有磷及/或硼合金或CoSi等之矽化物。又，作為上述金屬，可為其他易腐蝕性金屬之銅、鎢、鍺或此等之任一種的合金，作為該合金，可列舉銅及鎢之至少1種、與其他過渡元素及典型元素(例如磷、硼、矽等)之至少1種的合金，具體而言，例示有CuPB等之含有磷及/或硼合金或WSi、SiGe等之矽化物。使用後述之二烷醇羥胺及二烷醇胺時，不僅鈷即使對於銅、鎢、SiGe亦容易得到腐蝕抑制效果。以下，在本說明書，有時分別將「鈷或其合金」、「銅或其合金」及「鎢或其合金」單簡稱為「鈷」、「銅」及「鎢」。 [0017] 本實施態樣之洗淨液係藉由含有烷醇羥胺與烷醇胺，至少對於鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬，具有優異之腐蝕抑制機能。因此，基板之洗淨時，該洗淨液即使與基板表面之鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬接觸，亦良好地抑制鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬的腐蝕。針對其作用機構雖尚不清楚，但推測是藉由烷醇羥胺與烷醇胺所具有之還原作用，抑制鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬的腐蝕。而且，非常清楚烷醇羥胺與烷醇胺的混合物與烷醇胺單獨的情況相比，其防腐蝕效果大。 [0018] 又，烷醇羥胺與烷醇胺相比，由於蒸氣壓低，即使為將洗淨液昇溫至特定的溫度進行洗淨的情況，亦能抑制組成變化，作為洗淨液為有用。例如適合使用蒸氣壓較佳為0.3mmHg以下，更佳為0.1mmHg，再更佳為0.05mmHg以下之烷醇羥胺。藉由併用具有如此之性質的烷醇羥胺與烷醇胺，可得到較單獨使用烷醇胺時，防腐蝕效果更高，且有用的洗淨液。 [0019] 進而，烷醇羥胺與烷醇胺相比，由於水溶性高，對溶媒和溶劑可使用成本低廉的水，又，在藉由該水溶液所致之洗淨可抑制殘渣，作為洗淨液為有用。例如，適合使用LogP較佳為0.5以下之烷醇羥胺。藉由併用具有如此之性質之烷醇羥胺與烷醇胺，可得到較單獨使用烷醇胺時，防腐蝕效果更高，且有用的洗淨液。 [0020] LogP值係意指辛醇/水分配係數，可使用Ghose、Pritchett、Crippen等之參數，藉由計算算出(參照J.Comp.Chem.,9,80(1998))。此計算可使用如CAChe 6.1(富士通股份有限公司製)之軟體進行。 [0021] 以下，詳細說明本實施形態之洗淨液的各成分。 [0022] ＜烷醇羥胺＞ 作為烷醇羥胺，係使用上述一般式(1)表示之烷醇羥胺。式中，Ra1
及Ra2
分別獨立表示具有1～3個羥基之碳原子數1～10之烷基或氫原子。惟，Ra1
及Ra2
不會同時成為氫原子。 [0023] 作為烷醇羥胺，較佳為Ra1
及Ra2
為具有1～3個羥基之碳原子數1～10之烷基之二烷醇羥胺。使用如此之烷醇羥胺，以不僅對於鈷，亦得到對於銅或鎢、SiGe等之矽化物其他易腐蝕性金屬之腐蝕抑制效果的點來看較佳。 [0024] 在Ra1
及Ra2
之羥基，可分別為1個或2個，即使1個亦可充分發揮本發明的效果。在Ra1
及Ra2
之羥基，係在Ra1
及Ra2
之各烷基的碳原子數為3時，可構成第一級醇或第二級醇之任一種，又，在Ra1
及Ra2
之各烷基的碳原子數為4～10時，雖可構成第一級醇、第二級醇或第三級醇之任一種，但較佳為構成第二級醇。 [0025] 作為在Ra1
及Ra2
之碳原子數1～10之烷基，可為直鏈狀、分枝狀或環狀之任一種烷基，例如可列舉甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、環丁基、n-戊基、異戊基、sec-戊基、tert-戊基、新戊基、2-甲基丁基、1,2-二甲基丙基、1-乙基丙基、環戊基、n-己基、異己基、sec-己基、tert-己基、新己基、2-甲基戊基、1,2-二甲基丁基、2,3-二甲基丁基、1-乙基丁基、環己基、n-庚基、n-辛基、n-壬基、n-癸基等，較佳為碳原子數1～4之直鏈狀或分枝狀之烷基，特佳為乙基、n-丙基、異丙基。 [0026] 作為在Ra1
及Ra2
之具有1～3個羥基之碳原子數1～4之直鏈狀或分枝狀的烷基之具體例，例如可列舉1-羥基乙基、2-羥基乙基、1,2-二羥基乙基、2,2-二羥基乙基、1-羥基-n-丙基、2-羥基-n-丙基、3-羥基-n-丙基、1,2-二羥基-n-丙基、1,3-二羥基-n-丙基、2,2-二羥基-n-丙基、2,3-二羥基-n-丙基、3,3-二羥基-n-丙基、1,2,3-三羥基-n-丙基、2,2,3-三羥基-n-丙基、2,3,3-三羥基-n-丙基、1-羥基異丙基、2-羥基異丙基、1,1-二羥基異丙基、1,2-二羥基異丙基、1,3-二羥基異丙基、1,2,3-三羥基異丙基、1-羥基-n-丁基、2-羥基-n-丁基、3-羥基-n-丁基、4-羥基-n-丁基、1,2-二羥基-n-丁基、1,3-二羥基-n-丁基、1,4-二羥基-n-丁基、2,2-二羥基-n-丁基、2,3-二羥基-n-丁基、2,4-二羥基-n-丁基、3,3-二羥基-n-丁基、3,4-二羥基-n-丁基、4,4-二羥基-n-丁基、1,2,3-三羥基-n-丁基、1,2,4-三羥基-n-丁基、1,3,4-三羥基-n-丁基、2,2,3-三羥基-n-丁基、2,2,4-三羥基-n-丁基、2,3,3-三羥基-n-丁基、3,3,4-三羥基-n-丁基、2,4,4-三羥基-n-丁基、3,4,4-三羥基-n-丁基、2,3,4-三羥基-n-丁基、1-羥基-sec-丁基、2-羥基-sec-丁基、3-羥基-sec-丁基、4-羥基-sec-丁基、1,1-二羥基-sec-丁基、1,2-二羥基-sec-丁基、1,3-二羥基-sec-丁基、1,4-二羥基-sec-丁基、2,3-二羥基-sec-丁基、2,4-二羥基-sec-丁基、3,3-二羥基-sec-丁基、3,4-二羥基-sec-丁基、4,4-二羥基-sec-丁基、1-羥基-2-甲基-n-丙基、2-羥基-2-甲基-n-丙基、3-羥基-2-甲基-n-丙基、1,2-二羥基-2-甲基-n-丙基、1,3-二羥基-2-甲基-n-丙基、2,3-二羥基-2-甲基-n-丙基、3,3-二羥基-2-甲基-n-丙基、3-羥基-2-羥基甲基-n-丙基、1,2,3-三羥基-2-甲基-n-丙基、1,3,3-三羥基-2-甲基-n-丙基、2,3,3-三羥基-2-甲基-n-丙基、1,3-二羥基-2-羥基甲基-n-丙基、2,3-二羥基-2-羥基甲基-n-丙基、1-羥基-2-甲基異丙基、1,3-二羥基-2-甲基異丙基、1,3-二羥基-2-羥基甲基異丙基等，特佳為2-羥基乙基、2-羥基-n-丙基、2-羥基異丙基。 [0027] 烷醇羥胺相對於烷醇羥胺與烷醇胺之合計的含量，較佳為0.01～99.9質量%，更佳為1～90質量%，再更佳為10～70質量%。藉由成為如此之含量，可邊抑制易腐蝕性金屬，尤其是鈷、銅、鎢、SiGe等之矽化物的腐蝕，邊有效果地去除被洗淨物。 [0028] 又，烷醇羥胺的含量，相對於洗淨液全量，較佳為0.001～10質量%，更佳為0.01～5質量%，再更佳為0.01～0.5質量%。藉由成為如此之含量，可邊抑制易腐蝕性金屬，尤其是鈷、銅、鎢、SiGe等之矽化物的腐蝕，邊有效果地去除被洗淨物。 [0029] ＜烷醇胺＞ 作為烷醇胺，使用上述一般式(2)表示之烷醇胺。式(2)中，Rb1
及Rb2
分別獨立表示具有1～3個羥基之碳原子數1～10之烷基或氫原子。惟，Rb1
及Rb2
不會同時成為氫原子。 [0030] 作為烷醇胺，較佳為Rb1
及Rb2
為具有1～3個羥基之碳原子數1～10之烷基的二烷醇羥胺。使用如此之烷醇胺，以不僅對於鈷，亦得到對於銅或鎢、SiGe等之矽化物其他易腐蝕性金屬之腐蝕抑制效果的點來看較佳。 [0031] 作為在Rb1
及Rb2
之羥基，係與針對在一般式(1)之Ra1
及Ra2
之羥基所說明者同樣，在Rb1
及Rb2
之各烷基的碳原子數為3時，又，在Rb1
及Rb2
之各烷基的碳原子數為4～10時，較佳為構成第二級醇。 [0032] 作為在Rb1
及Rb2
之碳原子數1～10之烷基，可列舉與一般式(1)說明者同樣者，較佳為碳原子數1～4之直鏈狀或分枝狀之烷基，特佳為乙基、n-丙基、異丙基。 [0033] 作為在Rb1
及Rb2
之具有1～3個羥基之碳原子數1～4之直鏈狀或分枝狀的烷基之具體例，可列舉與一般式(1)說明者同樣者，特佳為2-羥基乙基、2-羥基-n-丙基。 [0034] 又，烷醇胺的含量，相對於洗淨液全量，較佳為0.001～10質量%，更佳為0.01～3質量%，再更佳為0.01～0.5質量%。藉由成為如此之含量，可邊抑制鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬的腐蝕，邊去除被洗淨物。 [0035] ＜溶劑＞ 溶劑較佳為含有水，作為水，可使用純水、脫離子水、離子交換水等。溶劑，又，除了水之外，為了提昇烷醇羥胺及烷醇胺的溶解性，亦可使用水溶性有機溶劑。作為水溶性有機溶劑，可使用該領域慣用之化合物。水溶性有機溶劑可單獨使用，亦可組合2種以上使用。溶劑較佳為併用水與水溶性有機溶劑。作為溶劑，併用水與水溶性有機溶劑時，水相對於水與水溶性有機溶劑的合計的含量較佳為1～99質量%，更佳為10～40質量%，再更佳為15～30質量%。 [0036] 作為水溶性有機溶劑，例如可列舉二甲基亞碸等之亞碸類；二甲基碸、二乙基碸、雙(2-羥基乙基)碸、四亞甲基碸等之碸類；N,N-二甲基甲醯胺、N-甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基乙醯胺、N,N-二乙基乙醯胺等之醯胺類；N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-羥基甲基-2-吡咯烷酮、N-羥基乙基-2-吡咯烷酮等之內醯胺類；β-丙內酯、γ-丁內酯、γ-戊內酯、δ-戊內酯、γ-己內酯、ε-己內酯等之內酯類；1,3-二甲基-2-四氫咪唑酮、1,3-二乙基-2-四氫咪唑酮、1,3-二異丙基-2-四氫咪唑酮等之四氫咪唑酮類；乙二醇、丙二醇、1,2-丁二醇、1,3-丁二醇、2,3-丁二醇、甘油、二乙二醇等之多元醇類；乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、乙二醇單烯丙基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、3-甲氧基-3-甲基-1-丁醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、二乙二醇單苄基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單丙基醚、二丙二醇單丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、三乙二醇單丙基醚、三乙二醇單丁基醚、三丙二醇單丁基醚等之甘醇單烷基醚類、乙二醇二甲基醚、二乙二醇二甲基醚、三乙二醇二甲基醚、四乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚等之甘醇二烷基醚類等之甘醇醚系溶劑；乙二醇單乙酸酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單乙酸酯等之甘醇酯系溶劑。 [0037] 其中，選擇作為較佳之水溶性有機溶劑，係選自由二丙二醇單甲基醚(DPM)、丙二醇(PG)、3-甲氧基-3-甲基-1-丁醇、二甲基亞碸、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、二乙二醇單乙基醚(乙基二甘醇)及二乙二醇單丁基醚所構成之群組中之至少1種。 [0038] 含有水溶性有機溶劑時，其含量，相對於洗淨液全量，較佳為1～99質量%，更佳為10～85質量%，再更佳為30～80質量%。藉由成為如此之含量，可邊抑制易腐蝕性金屬，尤其是鈷、銅、鎢、SiGe等之矽化物的腐蝕，邊有效果地去除被洗淨物。 [0039] ＜鹼性化合物＞ 作為鹼性化合物，若為烷醇羥胺及烷醇胺以外，具有洗淨機能者，則並未特別限定。例如作為鹼性化合物，較佳為使用選自由第4級氫氧化銨、上述一般式(1)表示之烷醇羥胺以外之羥胺化合物、烷基胺及氨所構成之群組中之至少一個。鹼性化合物可單獨使用，亦可組合2種以上使用。 [0040] [第4級氫氧化銨] 作為鹼性化合物，例如可使用第4級氫氧化銨。作為第4級氫氧化銨，較佳為下述一般式(3)表示之化合物。 [0041][0042] 上述一般式(3)中，Rc1
～Rc4
分別獨立表示碳原子數1～16之烷基、碳原子數6～16之芳基、碳原子數7～16之芳烷基、或碳原子數1～16之羥基烷基。 [0043] 上述一般式(3)表示之化合物當中，選自由四甲基氫氧化銨(TMAH)、四乙基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨、甲基三丙基氫氧化銨、甲基三丁基氫氧化銨、乙基三甲基氫氧化銨、二甲基二乙基氫氧化銨、苄基三甲基氫氧化銨、十六烷基三甲基氫氧化銨及(2-羥基乙基)三甲基氫氧化銨所構成之群組中之至少1種，從容易取得的點來看為特佳。進而，四甲基氫氧化銨及四乙基氫氧化銨從對於被洗淨物之溶解性高且洗淨性能高的點來看較佳。 [0044] [無機鹼] 又，作為鹼性化合物，例如可將無機鹼與第4級氫氧化銨併用。作為無機鹼，較佳為氫氧化鉀、氫氧化鈉、氫氧化銣等之鹼金屬之氫氧化物，更佳為氫氧化鉀。 [0045] [羥胺化合物] 又，作為鹼性化合物，例如可使用一般式(1)表示之烷醇羥胺以外之羥胺化合物。作為羥胺化合物，可列舉羥胺(HO-NH2
)、N-甲基羥胺、N,N-二乙基羥胺、N-乙基羥胺、N,N-二甲基羥胺、N-(tert-丁基)羥胺、N-丙基羥胺等。 [0046] [烷基胺] 又，作為鹼性化合物，例如可使用烷基胺。作為烷基胺化合物，可列舉N-甲基胺、N,N-二乙基胺、N-乙基胺、N,N-二甲基胺、N-(tert-丁基)胺、N-丙基胺等。 [0047] [其他鹼性化合物] 又，作為鹼性化合物，亦可使用氨。 [0048] 鹼性化合物的含量雖因化合物鹼性的強度而有所不同，但相對於洗淨液全量，較佳為0.5～30質量%，更佳為1～20質量%。藉由成為如此之含量，可邊抑制易腐蝕性金屬，尤其是鈷、銅、鎢、SiGe等之矽化物的腐蝕，邊有效果地去除被洗淨物。尚，將無機鹼與第4級氫氧化銨併用時，無機鹼的含量，相對於洗淨液全量，較佳為0.1質量ppm～1質量%，更佳為1質量ppm～1000質量ppm。藉由成為如此之含量，可邊抑制易腐蝕性金屬，尤其是鈷、銅、鎢、SiGe等之矽化物的腐蝕，邊有效果地去除被洗淨物。 [0049] ＜酸性化合物＞ 洗淨液為酸性時，摻合在洗淨液之酸性化合物於不阻礙本發明的目的的範圍，可從質子酸適當選擇。作為適合之酸性化合物的具體例，可列舉鹽酸、氫氟酸、硫酸、硝酸、蟻酸、乙酸、丙酸、丁酸、異丁酸、戊酸、異戊酸、乳酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、檸檬酸、甘醇酸、二甘醇酸、磷酸、甲烷磺酸、三氟乙酸、三氟甲烷磺酸等之質子酸。酸性化合物可組合2種以上使用。 [0050] 對酸性化合物之洗淨液的摻合量雖因化合物之酸性的強度而有所不同，但通常情況為相對於洗淨液全量，較佳為0.1～20質量%，更佳為0.5～15質量%。再更佳為1.0～10質量%。藉由成為如此之含量，可邊抑制易腐蝕性金屬，尤其是鈷、銅、鎢、SiGe等之矽化物的腐蝕，邊有效果地去除被洗淨物。 [0051] ＜其他成分＞ 本實施態樣之洗淨液中，在不損害本發明的效果的範圍，可添加界面活性劑等之其他成分。作為界面活性劑，並未特別限定，例如可列舉非離子系界面活性劑、陰離子系界面活性劑、陽離子系界面活性劑、兩性界面活性劑等。 [0052] 又，本實施態樣之洗淨液若為含有上述之一般式(1)表示之烷醇羥胺與一般式(2)表示之烷醇胺者，雖不需要含有其他防腐蝕劑，但亦可為含有其他防腐蝕劑者。作為該其他防腐蝕劑，雖並未特別限定，但例如除了苯并三唑、胺基四唑、5-胺基-1-苯基四唑、5-胺基-1-(1-萘基)四唑、1-甲基-5-胺基四唑、1,5-二胺基四唑、咪唑、吲哚、嘌呤、吡唑、吡啶、嘧啶、吡咯、吡咯烷、吡咯啉等之含氮雜環化合物之外，可列舉2級胺系化合物、胺基酸系化合物等。 [0053] ＜＜防腐蝕劑＞＞ 本發明之防腐蝕劑為含有上述一般式(1)表示之烷醇羥胺與上述一般式(2)表示之烷醇胺之組成物，該組成物(典型上為液狀組成物)適合作為防腐蝕劑。 [0054] 又，本實施態樣之防腐蝕劑，較佳為在上述一般式(1)之Ra1
與在上述一般式(2)之Rb1
為同一基，在上述一般式(1)之Ra2
與在上述一般式(2)之Rb2
為同一基。又，本實施態樣之防腐蝕劑較佳為在上述一般式(1)之Ra1
與Ra2
為同一基，在上述一般式(2)之Rb1
與Rb2
為同一基，更佳為Ra1
、Ra2
、Rb1
及Rb2
為同一基。 [0055] 本實施態樣之防腐蝕劑如上述，藉由使用烷醇羥胺與烷醇胺的混合物，可有效果地抑制金屬，尤其是鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬的腐蝕。 [0056] ＜＜製造洗淨液或防腐蝕劑之方法＞＞ 製造本發明之洗淨液或防腐蝕劑之方法，係一種方法，其係製造含有上述一般式(1)表示之烷醇羥胺之洗淨液或防腐蝕劑之方法，其係包含藉由氧化上述一般式(2)表示之烷醇胺，來合成該烷醇羥胺。製造本發明之洗淨液或防腐蝕劑之方法，適合作為製造本發明之第1態樣之洗淨液或本發明之第2態樣之防腐蝕劑之方法。 [0057] 作為氧化烷醇胺之氧化劑，可列舉過氧化氫等。 [0058] 氧化劑相對於烷醇胺的添加量，相對於烷醇胺的莫耳量，較佳為30～100莫耳%，更佳為60～80莫耳%。藉由成為如此之含量，從烷醇胺生成烷醇羥胺，可得到具有高防腐蝕效果之混合液。 [0059] 氧化烷醇胺之反應溫度，例如較佳為40～80℃，更佳為50～70℃。又，反應時間較佳為20～120分鐘，更佳為30～90分鐘。藉由於如此之條件下進行氧化反應，從烷醇胺生成烷醇羥胺，可得到具有高防腐蝕效果之混合液。 [0060] 根據此方法，容易得到出發物質之烷醇胺、與反應生成物之烷醇羥胺的混合物，並非將氧化反應後所得之該混合物直接使用，亦即單離純化烷醇胺或烷醇羥胺，而是可使用在本實施態樣之洗淨液或防腐蝕劑，製造效率良好。又，與單獨將烷醇胺或烷醇羥胺使用在洗淨液或防腐蝕劑的情況相比，可得到具有高防腐蝕效果之洗淨液或防腐蝕劑。 [0061] 例如，如下述之反應式所示，藉由於烷醇胺之二乙醇胺添加過氧化氫水(H2
O2
)進行氧化，可得到下述構造式所示之反應生成物(烷醇羥胺即2,2’-(羥基亞胺基)雙乙醇)。惟，在下述反應，氧化二乙醇胺的全量為困難，所得之反應液成為二乙醇胺與2,2’-(羥基亞胺基)雙乙醇的混合物。烷醇羥胺即2,2’-(羥基亞胺基)雙乙醇的收率雖亦因反應條件而異，但為25%～70%左右。 [0062][0063] ＜＜洗淨方法＞＞ 使用本發明之洗淨液之洗淨方法，亦為本發明之一。 本發明之洗淨方法，係使用上述之洗淨液、防腐蝕劑或藉由上述方法製造之洗淨液或防腐蝕劑洗淨基板之使用洗淨液，來洗淨基板之方法。 [0064] 該基板之洗淨適合作為在光刻之基板的洗淨。 例如，本實施形態之洗淨方法，係在於基板的表面形成特定圖型之蝕刻遮罩層的蝕刻遮罩層形成步驟，蝕刻自上述蝕刻遮罩層露出之上述基板的蝕刻步驟之後步驟進行，洗淨經蝕刻之上述基板之方法。本實施形態之洗淨方法適合基板的表面的至少一部分為由鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬所構成的情況。此時，上述基板的表面中雖已露出鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬的至少一部分，與洗淨液接觸，但鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬的腐蝕良好地抑制。因此，藉由使用上述之洗淨液進行洗淨，可邊抑制鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬的腐蝕，邊有效果地去除被洗淨物。 [0065] 如後述，本實施形態之洗淨方法，根據蝕刻速度的評估，相對於鈷為小至0.2 nm/min以下，較佳為0.1 nm/min以下，更佳為0.09 nm/min以下，腐蝕抑制效果大。又，同樣，根據蝕刻速度的評估，相對於銅可小至0.4 nm/min以下，較佳為0.2 nm/min以下，更佳為0.04 nm/min以下，可期待腐蝕抑制效果。又，同樣地，根據蝕刻速度的評估，相對於鎢可小至0.2 nm/min以下，較佳為0.1 nm/min以下，更佳為0.01 nm/min以下，可期待腐蝕抑制效果。又，同樣地，根據蝕刻速度的評估，相對於SiGe可小至0.05 nm/min以下，較佳為0.01 nm/min以下，可期待腐蝕抑制效果。使用上述之二烷醇羥胺及二烷醇胺時，不僅鈷，即使對於銅、鎢、SiGe等之矽化物其他易腐蝕性金屬亦容易得到腐蝕抑制效果。 [0066] 具體之洗淨方法，若為通常進行之方法則並未特別限定。例如使用浸漬法、槳法，淋浴法等，藉由於上述之洗淨液使基板接觸1～40分鐘來處理。洗淨通常雖於室溫進行，但為了提高洗淨效果，亦可將洗淨液昇溫至85℃左右來進行。 [0067] ＜＜防腐蝕方法＞＞ 如此，使用上述之洗淨液、防腐蝕劑或藉由上述方法製造之洗淨液或防腐蝕劑，防腐蝕易腐蝕性金屬之方法，亦為本發明之一。該防腐蝕方法，例如包含將鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬(例如於表面露出該易腐蝕性金屬之基板)與該洗淨液或防腐蝕劑接觸，具體而言可與上述之洗淨方法同樣地進行。 [0068] 又，使用上述之防腐蝕劑或藉由上述方法所製造之防腐蝕劑，防腐蝕易腐蝕性金屬之方法，係包含藉由將該防腐蝕劑添加在洗淨液、顯影液、淋洗液、剝離液等之光刻用藥液等，包含在光刻用藥液，例如將鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬(例如於表面露出該易腐蝕性金屬之基板)與該光刻用藥液接觸。該防腐蝕方法係例如，因應包含該防腐蝕劑之洗淨液、顯影液、淋洗液、剝離液等之光刻用藥液的種類和用途，可使用光刻法所通常使用之洗淨方法(例如上述之洗淨方法)、顯影方法、淋洗方法、剝離方法。作為包含本實施態樣之防腐蝕劑之光刻用藥液，較佳為洗淨液、顯影液。作為該顯影液，例如可使用四甲基氫氧化銨(TMAH)2.38%水溶液等之鹼顯影液。 [0069] 包含本發明之防腐蝕劑之光刻用藥液，亦為本發明之一。作為該光刻用藥液，例如可列舉洗淨液、顯影液、淋洗液、剝離液等，較佳為洗淨液。 [0070] ＜＜製造半導體之方法＞＞ 包含使用本發明之洗淨方法之製造半導體的方法，亦為本發明之一。 製造本發明之半導體之方法，係包含使用上述之洗淨方法，來洗淨基板之製造包含基板之半導體之方法。 [0071] 根據本實施態樣之方法，如上述，基板的表面之至少一部分為由鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬所構成的情況，亦可抑制鈷、銅、鎢、SiGe等之矽化物其他易腐蝕性金屬的腐蝕，來製造半導體。 [0072] ＜＜光刻方法＞＞ 包含使用本發明之洗淨方法或本發明之防腐蝕方法的光刻方法，亦為本發明之一。作為本發明之防腐蝕方法，可為使用上述之洗淨液、防腐蝕劑或藉由上述方法製造之洗淨液或防腐蝕劑，防腐蝕易腐蝕性金屬之方法，亦可為包含將該防腐蝕劑包含在洗淨液、顯影液、淋洗液、剝離液等之光刻用藥液，將易腐蝕性金屬(例如於表面露出該易腐蝕性金屬之基板)與該光刻用藥液接觸之上述防腐蝕方法。 [實施例] [0073] 以下，雖將本發明藉由實施例詳細說明，但本發明並非被限定於此等之實施例。 [0074] [對照例] 作為對照例，準備由乙基二甘醇75.0質量%、四甲基氫氧化銨TMAH)2.0質量%、水(剩餘部分)23.0質量%所構成之溶液。 [0075] [實施例1～4] 於實施例，以表1所示的量，於分別溶解於水之烷醇胺(單乙醇胺、二乙醇胺、單異丙醇胺、二異丙醇胺)將過氧化氫水(H2
O2
)於60℃攪拌下耗費60分鐘滴下。而且，於60℃進一步反應1小時後，將所得之反應液以相對於成為對照例之溶液99.5質量份，分別成為0.5質量份的方式添加，來調製洗淨液。 [0076] 例如，實施例1之洗淨液的組成為乙基二甘醇75.0質量份、四甲基氫氧化銨(TMAH)2.0質量份、上述之反應液0.5質量份及水(剩餘部分)22.5質量份。 [0077] 在實施例1～4於烷醇胺添加過氧化氫水所得之反應液，係如表3所示，為出發物質之烷醇胺、與氧化反應之生成物之烷醇羥胺的混合物一事，皆藉由液體層析質量分析法(LC-MS)確認。 [0078] 表示分析結果之一例。於實施例4所得之反應液，藉由液體層析質量分析法(LC-MS)評估之結果，於m/z值成為134.1172、150.1122之位置觀察到峰值。由此結果，瞭解到於實施例4所得之反應液為出發物質之二異丙醇胺、與作為氧化反應之生成物，於氮原子鍵結一個羥基而成之二異丙醇羥胺的混合物。又，將此實施例4之反應液藉由核磁共振裝置(NMR)評估的結果，確認出發物質：反應生成物=59：41的莫耳比，二異丙醇羥胺的收率為32.2%。 [0079] [實施例5] 作為洗淨液，相對於四甲基氫氧化銨(TMAH)2.38%之水溶液(商品名：NMD-3、東京應化工業公司製)100質量%，添加1.0質量%於實施例4所得之反應液，來調製洗淨液。 [0080] [實施例6] 作為洗淨液，相對於包含四甲基氫氧化銨(TMAH) 2.38%與界面活性劑之水溶液(商品名：NMD-W、東京應化工業公司製)100質量%，添加1.0質量%於實施例4所得之反應液，來調製洗淨液。 [0081] [實施例7] 作為洗淨液，於由二丙二醇單甲基醚(DPM)65質量%、丙二醇(PG)5質量%、四甲基氫氧化銨(TMAH)2.0質量%及水(剩餘部分)28質量%所構成之混合溶液，添加1.0質量%於實施例4所得之反應液，來調製洗淨液。 [0082] [比較例1～6] 於比較例1～6，如表2所示，作為防腐蝕劑之比較對照化合物，將混合單乙醇胺、二乙醇胺、二乙基胺、單異丙醇胺、二異丙醇胺、二丙基胺與水所得之混合物各0.5質量份，相對於成為對照例之溶液99.5質量份進行添加，來調製洗淨液。 [0083] [比較例7] 於比較例7，以表1所示的量，作為防腐蝕劑之比較對照化合物，相對於溶解於水之二丙基胺將過氧化氫水(H2
O2
)於60℃攪拌下耗費60分鐘滴下。而且，於60℃進一步反應1小時後，將所得之反應液以相對於成為對照例之溶液99.5質量份，成為0.5質量份的方式添加，來調製洗淨液。於比較例7所得之反應液係如表4所示，為二丙基胺與二丙基羥胺的混合物。 [0084] [比較例8] 除了未添加於實施例4所得之反應液之外，其他與實施例5同樣地調製洗淨液。 [0085] [比較例9] 除了未添加於實施例4所得之反應液之外，其他與實施例6同樣地調製洗淨液。 [0086] [比較例10] 除了未添加於實施例4所得之反應液之外，其他與實施例7同樣地調製洗淨液。 [0087][0088][0089] [相對於銅層、鎢層或鈷層之蝕刻速度的評估] 將銅、鎢或鈷成膜在矽基板上，得到具備厚度100nm之銅層、鎢層或鈷層的矽基板。將此矽基板浸漬在加溫至60℃之洗淨液60分鐘。浸漬結束後，將矽基板以純水淋洗，測定銅層、鎢層或鈷層的膜厚，從浸漬前後之膜厚的差求得銅層、鎢層或鈷層的蝕刻速度。將其結果示於表3、4。 [0090] 表3、4中之蝕刻速度的評估係根據下述之基準。尚，藉由對照例之溶液所得的蝕刻速度係銅層為2.21、鎢層為0.14、鈷層為0.35。蝕刻速度之評估的單位為[ nm/min]。 ‧銅(Cu) ◎：0.2以下、〇：超過0.2且為0.4以下、×：超過0.4 ‧鎢(W) ◎：0.1以下、〇：超過0.1且為0.2以下、×：超過0.2 ‧鈷(Co) ◎：0.1以下、〇：超過0.1且為0.2以下、×：超過0.2 [0091][0092][0093] 由表3、4之結果，於包含烷醇羥胺與烷醇胺的混合液之實施例1～4的洗淨液，與未包含烷醇羥胺之比較例1～7的洗淨液相比，鈷的蝕刻速度皆小，腐蝕抑制機能優異。其中，於包含二烷醇羥胺與二烷醇胺的混合液之實施例2、4的洗淨液，與比較例1～7的洗淨液相比，銅或鎢的蝕刻速度亦小，腐蝕抑制機能亦優異。尚，確認於實施例所得之烷醇羥胺，皆較於比較例所使用之胺，LogP值更大且水溶性優異，且蒸氣壓低，組成安定性優異。 [0094] [對於SiGe層之蝕刻速度的評估] 將具有厚度100nm之SiGe層的矽基板浸漬於實施例5～7及比較例8～10之洗淨液(25℃)10分鐘。浸漬結束後，將矽基板以純水淋洗，測定SiGe層的膜厚，從浸漬前後之膜厚的差求得SiGe層的蝕刻速度。將其結果示於表5。 [0095] 表5中之蝕刻速度的評估係根據下述之基準。蝕刻速度之評估的單位為[ nm/min]。 ‧SiGe ◎：0.01以下、〇：超過0.01且為0.05以下、×：超過0.05 [0096][0097] 由表5之結果，於使用於包含烷醇羥胺與烷醇胺的混合液之實施例4所得之反應液的實施例5～7的洗淨液，與未包含烷醇羥胺(1,1’(羥基亞胺基)雙(2-丙醇))之比較例8～10的洗淨液相比，確認即使對於SiGe層，蝕刻速度皆小，腐蝕抑制機能優異。<<Cleaning solution>> The cleaning solution of the present invention contains alkanolhydroxylamine represented by the general formula (1) above (in this specification, it may simply be simply referred to as "alkanolhydroxylamine"), and the general formula above. (2) The alkanolamine (in this specification, it may be simply referred to as "alkanolamine"), solvent, and the alkanolhydroxylamine and basic compounds other than the alkanolamine (in this specification, it may be simply referred to as "alkanolamine") It is a composition of either a "basic compound") or an acidic compound, and the composition (typically a liquid composition) is suitable as a cleaning solution and an anticorrosion agent. Furthermore, in the cleaning solution of this embodiment, it is preferable that R a1 in the above general formula (1) and R b1 in the above general formula (2) are the same base, and R in the above general formula (1) is the same base. a2 is the same group as R b2 in the above general formula (2). Furthermore, in the cleaning solution of the present embodiment, it is preferable that R a1 and R a2 in the above general formula (1) are the same group, and R b1 and R b2 in the above general formula (2) are the same group, more preferably R a1 , R a2 , R b1 and R b2 are the same group. [0015] The cleaning solution is suitable as a cleaning solution for electronic components such as semiconductor devices and liquid crystal displays (LCDs). For example, it is suitable as a photolithography step, an etching step, a FEOL (Front End of Line) step such as a chemical mechanical polishing (CMP) step or a BEOL (Back End of Line) step such as a wiring formation step in a semiconductor manufacturing step, or Through-silicon electrode (TSV), or C4 process (Controlled Collapse Chip Connection), the cleaning solution used in subsequent steps is suitable for cleaning substrates with metal surfaces. The so-called substrate having metal on the surface refers to a substrate in which metal is exposed on at least a part of the surface of the substrate. The metal is, for example, a metal formed in a metal wiring layer, a plug, and other metal structures that form a substrate of a semiconductor device. As the substrate, a metal wiring layer, a low dielectric material layer, an insulating layer, etc. are laminated on a substrate such as a silicon wafer to form a substrate of a semiconductor device, or the like. Moreover, as a board|substrate, the board|substrate provided with the silicide layer containing germanium etc. may be sufficient. The cleaning solution of this embodiment is suitable for lithography cleaning and lithography cleaning, and can be used as a lithography cleaning solution. [0016] As the above-mentioned metal, cobalt or an alloy thereof, which is a corrosive metal, can be exemplified. Cobalt alloys include alloys with at least one of other transition elements and typical elements (for example, phosphorus, boron, silicon, etc.), and specifically, phosphorus and/or boron-containing alloys such as CoWPB, and CoSi, etc. are exemplified. of silicide. In addition, the above-mentioned metal may be an alloy of copper, tungsten, germanium or any one of the other corrosive metals, and as the alloy, at least one of copper and tungsten, and other transition elements and typical elements ( For example, at least one alloy of phosphorus, boron, silicon, etc.), and specifically, silicides containing phosphorus and/or boron alloys such as CuPB, or silicides such as WSi and SiGe are exemplified. When dialkanolhydroxylamine and dialkanolamine described later are used, not only cobalt, but also copper, tungsten, and SiGe can easily obtain a corrosion inhibitory effect. Hereinafter, in this specification, "cobalt or its alloy", "copper or its alloy", and "tungsten or its alloy" may be simply referred to as "cobalt", "copper" and "tungsten", respectively. [0017] The cleaning solution of this embodiment contains alkanolhydroxylamine and alkanolamine, at least for silicides and other corrosive metals such as cobalt, copper, tungsten, SiGe, etc., has an excellent corrosion inhibition function. Therefore, during the cleaning of the substrate, even if the cleaning solution comes into contact with silicides such as cobalt, copper, tungsten, SiGe and other corrosive metals on the surface of the substrate, the silicides such as cobalt, copper, tungsten, and SiGe are well inhibited. Corrosion of other corrosive metals. Although its mechanism of action is still unclear, it is presumed that the reduction effect of alkanolhydroxylamine and alkanolamine inhibits the corrosion of silicides such as cobalt, copper, tungsten, SiGe and other corrosive metals. Furthermore, it became clear that the anticorrosion effect of the mixture of alkanolhydroxylamine and alkanolamine is greater than the case of alkanolamine alone. [0018] In addition, since alkanolhydroxylamine has a lower vapor pressure than alkanolamine, even in the case of cleaning by raising the temperature of the cleaning solution to a specific temperature, the composition change can be suppressed, and it is useful as a cleaning solution. For example, it is suitable to use alkanolhydroxylamine whose vapor pressure is preferably 0.3 mmHg or less, more preferably 0.1 mmHg, and still more preferably 0.05 mmHg or less. By using the alkanolhydroxylamine and alkanolamine having such properties together, a cleaning solution having a higher anticorrosion effect and usefulness can be obtained than when the alkanolamine is used alone. Furthermore, compared with alkanolamine, alkanolhydroxylamine has high water solubility, so that low-cost water can be used for the solvent and solvent, and the cleaning by the aqueous solution can suppress residues, and can be used as a cleaning agent. Liquid is useful. For example, it is suitable to use alkanolhydroxylamine whose LogP is preferably 0.5 or less. By using the alkanolhydroxylamine and the alkanolamine having such properties together, a cleaning solution having a higher anticorrosion effect and usefulness can be obtained than when the alkanolamine is used alone. The LogP value means the octanol/water partition coefficient, which can be calculated by using the parameters of Ghose, Pritchett, Crippen, etc. (refer to J.Comp.Chem., 9,80 (1998)). This calculation can be performed using software such as CAChe 6.1 (manufactured by Fujitsu Co., Ltd.). [0021] Hereinafter, each component of the cleaning solution of the present embodiment will be described in detail. <Alkanolhydroxylamine> As the alkanolhydroxylamine, the alkanolhydroxylamine represented by the above-mentioned general formula (1) was used. In the formula, R a1 and R a2 each independently represent an alkyl group having 1 to 3 hydroxyl groups and a carbon number of 1 to 10 or a hydrogen atom. However, R a1 and R a2 do not become hydrogen atoms at the same time. [0023] As the alkanolhydroxylamine, R a1 and R a2 are preferably dialkanolhydroxylamines having 1 to 3 hydroxyl groups and an alkyl group of 1 to 10 carbon atoms. The use of such an alkanolhydroxylamine is preferable in that a corrosion inhibitory effect is obtained not only with respect to cobalt but also with respect to silicides such as copper, tungsten, SiGe, and other corrosive metals. [0024] The hydroxyl groups of R a1 and R a2 can be respectively one or two, and even one can fully exert the effect of the present invention. The hydroxyl groups of R a1 and R a2 can constitute either a first-order alcohol or a second-order alcohol when the number of carbon atoms of each of the alkyl groups of R a1 and R a2 is 3. Moreover, in R a1 and R When the number of carbon atoms of each alkyl group of a2 is 4 to 10, it may constitute any one of the first-order alcohol, the second-order alcohol, or the third-order alcohol, but it preferably constitutes the second-order alcohol. As the alkyl group with 1 to 10 carbon atoms in R a1 and R a2 , it can be any alkyl group of straight chain, branched or cyclic, for example, methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neo Pentyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, cyclopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl, 2 -Methylpentyl, 1,2-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, etc., preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms, particularly preferably ethyl, n-propyl, and isopropyl. As specific examples of straight-chain or branched alkyl groups having 1 to 3 hydroxyl groups and 1 to 4 carbon atoms in R a1 and R a2 , for example, 1-hydroxyethyl, 2- Hydroxyethyl, 1,2-dihydroxyethyl, 2,2-dihydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1 ,2-dihydroxy-n-propyl, 1,3-dihydroxy-n-propyl, 2,2-dihydroxy-n-propyl, 2,3-dihydroxy-n-propyl, 3,3 -Dihydroxy-n-propyl, 1,2,3-trihydroxy-n-propyl, 2,2,3-trihydroxy-n-propyl, 2,3,3-trihydroxy-n-propyl , 1-hydroxyisopropyl, 2-hydroxyisopropyl, 1,1-dihydroxyisopropyl, 1,2-dihydroxyisopropyl, 1,3-dihydroxyisopropyl, 1,2,3 -Trihydroxyisopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl, 1,2-dihydroxy- n-butyl, 1,3-dihydroxy-n-butyl, 1,4-dihydroxy-n-butyl, 2,2-dihydroxy-n-butyl, 2,3-dihydroxy-n- Butyl, 2,4-dihydroxy-n-butyl, 3,3-dihydroxy-n-butyl, 3,4-dihydroxy-n-butyl, 4,4-dihydroxy-n-butyl , 1,2,3-trihydroxy-n-butyl, 1,2,4-trihydroxy-n-butyl, 1,3,4-trihydroxy-n-butyl, 2,2,3-trihydroxy Hydroxy-n-butyl, 2,2,4-trihydroxy-n-butyl, 2,3,3-trihydroxy-n-butyl, 3,3,4-trihydroxy-n-butyl, 2 ,4,4-trihydroxy-n-butyl, 3,4,4-trihydroxy-n-butyl, 2,3,4-trihydroxy-n-butyl, 1-hydroxy-sec-butyl, 2-hydroxy-sec-butyl, 3-hydroxy-sec-butyl, 4-hydroxy-sec-butyl, 1,1-dihydroxy-sec-butyl, 1,2-dihydroxy-sec-butyl , 1,3-dihydroxy-sec-butyl, 1,4-dihydroxy-sec-butyl, 2,3-dihydroxy-sec-butyl, 2,4-dihydroxy-sec-butyl, 3 ,3-dihydroxy-sec-butyl, 3,4-dihydroxy-sec-butyl, 4,4-dihydroxy-sec-butyl, 1-hydroxy-2-methyl-n-propyl, 2 -Hydroxy-2-methyl-n-propyl, 3-hydroxy-2-methyl-n-propyl, 1,2-dihydroxy-2-methyl-n-propyl, 1,3-dihydroxy -2-Methyl-n-propyl, 2,3-dihydroxy-2-methyl-n-propyl, 3,3-dihydroxy-2-methyl-n-propyl, 3-hydroxy-2 -Hydroxymethyl-n-propyl, 1,2,3-trihydroxy-2-methyl-n-propyl, 1,3,3-trihydroxy-2-methyl-n-propyl, 2, 3,3-Trihydroxy-2-methyl-n-propyl, 1,3-dihydroxy-2-hydroxymethyl-n-propyl, 2,3 -Dihydroxy-2-hydroxymethyl-n-propyl, 1-hydroxy-2-methylisopropyl, 1,3-dihydroxy-2-methylisopropyl, 1,3-dihydroxy-2 -Hydroxymethylisopropyl etc., 2-hydroxyethyl, 2-hydroxy-n-propyl, 2-hydroxyisopropyl are especially preferable. [0027] The content of the alkanolhydroxylamine relative to the sum of the alkanolhydroxylamine and the alkanolamine is preferably 0.01 to 99.9 mass %, more preferably 1 to 90 mass %, and still more preferably 10 to 70 mass %. With such a content, the object to be cleaned can be effectively removed while suppressing corrosion of corrosive metals, especially silicides such as cobalt, copper, tungsten, and SiGe. [0028] Furthermore, the content of alkanolhydroxylamine is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 0.5% by mass relative to the total amount of the cleaning solution. With such a content, the object to be cleaned can be effectively removed while suppressing corrosion of corrosive metals, especially silicides such as cobalt, copper, tungsten, and SiGe. <Alkanolamine> As the alkanolamine, the alkanolamine represented by the above-mentioned general formula (2) was used. In formula (2), R b1 and R b2 each independently represent an alkyl group having 1 to 3 hydroxyl groups and a carbon number of 1 to 10 or a hydrogen atom. However, R b1 and R b2 do not become hydrogen atoms at the same time. [0030] The alkanolamine is preferably a dialkanolhydroxylamine in which R b1 and R b2 are an alkyl group having 1 to 3 hydroxyl groups and an alkyl group having 1 to 10 carbon atoms. The use of such an alkanolamine is preferable from the viewpoint of obtaining a corrosion inhibitory effect not only on cobalt but also on silicides such as copper, tungsten, SiGe, and other corrosive metals. As the hydroxyl group at R b1 and R b2, the same as that described for the hydroxyl group of R b1 and R a2 in the general formula (1), the number of carbon atoms of each alkyl group at R b1 and R b2 is: In the case of 3, and when the number of carbon atoms in each of the alkyl groups of R b1 and R b2 is 4 to 10, it is preferable to constitute a second-order alcohol. As the alkyl group having 1 to 10 carbon atoms in R b1 and R b2 , the same as those described in the general formula (1) can be enumerated, preferably a straight chain or branched one having 1 to 4 carbon atoms. The alkyl group in this form is particularly preferably ethyl, n-propyl and isopropyl. As a specific example of a straight-chain or branched alkyl group having 1 to 3 hydroxyl groups and a straight-chain or branched alkyl group having 1 to 3 hydroxyl groups in R b1 and R b2 , the same as those described in the general formula (1) can be enumerated. Among them, particularly preferred are 2-hydroxyethyl and 2-hydroxy-n-propyl. [0034] Furthermore, the content of the alkanolamine is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, and still more preferably 0.01 to 0.5% by mass relative to the total amount of the cleaning solution. With such a content, the object to be cleaned can be removed while suppressing corrosion of silicides and other corrosive metals such as cobalt, copper, tungsten, and SiGe. <Solvent> The solvent preferably contains water, and as the water, pure water, deionized water, ion-exchanged water, or the like can be used. In addition to water, a water-soluble organic solvent can also be used as a solvent in order to improve the solubility of alkanolhydroxylamine and alkanolamine. As the water-soluble organic solvent, compounds conventionally used in this field can be used. The water-soluble organic solvent may be used alone or in combination of two or more. The solvent is preferably a combination of water and a water-soluble organic solvent. When water and a water-soluble organic solvent are used in combination as a solvent, the content of water with respect to the total of water and the water-soluble organic solvent is preferably 1 to 99% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 30% by mass quality%. As water-soluble organic solvent, for example can enumerate the sulfites such as dimethyl sulfite; Sulfur class; N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide amides such as amines; lactamides such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, etc. ; β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone and other lactones; 1,3-dimethyl- Tetrahydroimidazolones such as 2-tetrahydroimidazolone, 1,3-diethyl-2-tetrahydroimidazolone, 1,3-diisopropyl-2-tetrahydroimidazolone, etc.; ethylene glycol, propylene glycol , 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, glycerol, diethylene glycol and other polyols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether base ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoallyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether ether, 3-methoxy-3-methyl-1-butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono Butyl ether, diethylene glycol monobenzyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, Glycol monoalkyl ethers such as triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, etc., ethylene glycol dimethyl ether , diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, etc. Glycol ether solvents such as dialkyl ethers; ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetic acid Glycol ester solvents such as esters. Wherein, select as preferred water-soluble organic solvent, be selected from dipropylene glycol monomethyl ether (DPM), propylene glycol (PG), 3-methoxyl group-3-methyl-1-butanol, dimethyl ether The group consisting of ethylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol monoethyl ether (ethyl diethylene glycol) and diethylene glycol monobutyl ether At least 1 species from the group. [0038] When a water-soluble organic solvent is contained, its content is preferably 1 to 99% by mass, more preferably 10 to 85% by mass, and still more preferably 30 to 80% by mass relative to the total amount of the cleaning solution. With such a content, the object to be cleaned can be effectively removed while suppressing corrosion of corrosive metals, especially silicides such as cobalt, copper, tungsten, and SiGe. <Basic compound> The basic compound is not particularly limited as long as it has a cleaning function other than alkanolhydroxylamine and alkanolamine. For example, as the basic compound, it is preferable to use at least one selected from the group consisting of fourth-grade ammonium hydroxide, hydroxylamine compounds other than the alkanolhydroxylamine represented by the general formula (1), alkylamines, and ammonia. The basic compound may be used alone or in combination of two or more. [4th grade ammonium hydroxide] As the basic compound, for example, 4th grade ammonium hydroxide can be used. As the fourth-stage ammonium hydroxide, a compound represented by the following general formula (3) is preferred. [0041] In above-mentioned general formula (3), R c1 ～R c4 independently represent the alkyl group of carbon number 1～16, the aryl group of carbon number 6～16, the aralkyl group of carbon number 7～16, or a hydroxyalkyl group having 1 to 16 carbon atoms. Among the compounds represented by above-mentioned general formula (3), selected from tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltrimonium hydroxide Propyl ammonium hydroxide, methyl tributyl ammonium hydroxide, ethyl trimethyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide At least one kind selected from the group consisting of ammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide is particularly preferred in view of easy availability. Furthermore, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferable from the viewpoint of high solubility to the object to be cleaned and high cleaning performance. [Inorganic base] Further, as the basic compound, for example, an inorganic base can be used in combination with 4th order ammonium hydroxide. As the inorganic base, hydroxides of alkali metals such as potassium hydroxide, sodium hydroxide, and rubidium hydroxide are preferred, and potassium hydroxide is more preferred. [Hydroxyamine compound] Further, as the basic compound, for example, a hydroxylamine compound other than the alkanolhydroxylamine represented by the general formula (1) can be used. Examples of the hydroxylamine compound include hydroxylamine (HO-NH 2 ), N-methylhydroxylamine, N,N-diethylhydroxylamine, N-ethylhydroxylamine, N,N-dimethylhydroxylamine, N-(tert-butylene) group) hydroxylamine, N-propyl hydroxylamine, etc. [Alkylamine] Further, as the basic compound, for example, an alkylamine can be used. Examples of the alkylamine compound include N-methylamine, N,N-diethylamine, N-ethylamine, N,N-dimethylamine, N-(tert-butyl)amine, N- Propylamine, etc. [Other Basic Compounds] Further, as the basic compound, ammonia can also be used. [0048] Although the content of the basic compound varies depending on the strength of the basicity of the compound, it is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass relative to the total amount of the cleaning solution. With such a content, the object to be cleaned can be effectively removed while suppressing corrosion of corrosive metals, especially silicides such as cobalt, copper, tungsten, and SiGe. Furthermore, when the inorganic base is used together with the fourth-grade ammonium hydroxide, the content of the inorganic base is preferably 0.1 to 1 mass %, more preferably 1 to 1000 mass ppm, relative to the total amount of the cleaning solution. With such a content, the object to be cleaned can be effectively removed while suppressing corrosion of corrosive metals, especially silicides such as cobalt, copper, tungsten, and SiGe. <Acid Compound> When the cleaning solution is acidic, the acidic compound blended in the cleaning solution can be appropriately selected from protonic acids within the range that does not inhibit the purpose of the present invention. Specific examples of suitable acidic compounds include hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, lactic acid, oxalic acid, malonic acid, Protic acids such as succinic acid, glutaric acid, adipic acid, citric acid, glycolic acid, diglycolic acid, phosphoric acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, etc. The acidic compound may be used in combination of two or more. Although the compounding amount of the cleaning solution for the acidic compound varies depending on the strength of the acidity of the compound, it is usually 0.1 to 20 mass % relative to the total amount of the cleaning solution, more preferably 0.5% by mass. ~15% by mass. More preferably, it is 1.0 to 10 mass %. With such a content, the object to be cleaned can be effectively removed while suppressing corrosion of corrosive metals, especially silicides such as cobalt, copper, tungsten, and SiGe. <Other components> In the cleaning solution of the present embodiment, other components such as surfactants may be added within a range that does not impair the effects of the present invention. Although it does not specifically limit as a surfactant, For example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, etc. are mentioned. In addition, if the cleaning solution of this embodiment contains the alkanolhydroxylamine represented by the general formula (1) and the alkanolamine represented by the general formula (2), it is not necessary to contain other anticorrosion agents, but It may also contain other anti-corrosion agents. Although this other anticorrosion agent is not particularly limited, for example, benzotriazole, aminotetrazole, 5-amino-1-phenyltetrazole, 5-amino-1-(1-naphthyl) Nitrogen containing tetrazole, 1-methyl-5-aminotetrazole, 1,5-diaminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, etc. In addition to the heterocyclic compound, a secondary amine compound, an amino acid compound, etc. are mentioned. <<Anti-corrosion agent>> The anti-corrosion agent of the present invention is a composition containing an alkanolhydroxylamine represented by the above general formula (1) and an alkanolamine represented by the above general formula (2). liquid composition) is suitable as a corrosion inhibitor. In addition, in the anticorrosion agent of this embodiment, it is preferable that R a1 in the above-mentioned general formula (1) and R b1 in the above-mentioned general formula (2) are the same base, and R in the above-mentioned general formula (1) is the same base. a2 is the same group as R b2 in the above general formula (2). In addition, in the corrosion inhibitor of the present embodiment, R a1 and R a2 in the general formula (1) are preferably the same group, and R b1 and R b2 in the general formula (2) are the same group, more preferably R a1 , R a2 , R b1 and R b2 are the same group. The anti-corrosion agent of this embodiment is as described above, by using the mixture of alkanolhydroxylamine and alkanolamine, it can effectively inhibit the corrosion resistance of metals, especially silicides such as cobalt, copper, tungsten, SiGe, etc. Corrosion of metals. <<Method for producing a cleaning solution or anticorrosion agent>> The method for producing a cleaning solution or an anticorrosion agent of the present invention is a method for producing a cleaning solution containing the alkanolhydroxylamine represented by the general formula (1) above. A method for a clean solution or a corrosion inhibitor, which comprises synthesizing the alkanolhydroxylamine by oxidizing the alkanolamine represented by the general formula (2). The method of producing the cleaning solution or the anticorrosion agent of the present invention is suitable as a method of producing the cleaning solution of the first aspect of the present invention or the anticorrosion agent of the second aspect of the present invention. As the oxidizing agent for oxidizing alkanolamine, hydrogen peroxide etc. can be mentioned. [0058] The addition amount of the oxidizing agent relative to the alkanolamine, relative to the molar amount of the alkanolamine, is preferably 30-100 mol%, more preferably 60-80 mol%. By having such a content, the alkanolhydroxylamine is generated from the alkanolamine, and a mixed solution having a high anticorrosion effect can be obtained. [0059] The reaction temperature of the oxidized alkanolamine is, for example, preferably 40 to 80 °C, more preferably 50 to 70 °C. Moreover, the reaction time is preferably 20 to 120 minutes, more preferably 30 to 90 minutes. By performing oxidation reaction under such conditions, alkanolhydroxylamine is generated from alkanolamine, and a mixed solution having a high anticorrosion effect can be obtained. According to this method, easily obtain the mixture of the alkanolamine of starting material, and the alkanol hydroxylamine of reaction product, instead of directly using the mixture obtained after the oxidation reaction, i.e. singly purifying alkanolamine or alkanol Hydroxylamine can be used as a cleaning solution or an anticorrosion agent in this embodiment, and the production efficiency is good. Moreover, compared with the case where the alkanolamine or alkanolhydroxylamine is used alone in the cleaning solution or the anticorrosion agent, a cleaning solution or an anticorrosion agent having a high anticorrosion effect can be obtained. For example, as shown in the following reaction formula, by adding hydrogen peroxide water (H 2 O 2 ) to the diethanolamine of alkanolamine to oxidize, the reaction product (alkanol) shown in the following structural formula can be obtained. Hydroxylamine is 2,2'-(hydroxyimino)bisethanol). However, in the following reaction, it is difficult to oxidize the total amount of diethanolamine, and the obtained reaction solution becomes a mixture of diethanolamine and 2,2'-(hydroxyimino)diethanol. Although the yield of 2,2'-(hydroxyimino)diethanol of alkanolhydroxylamine also varies depending on the reaction conditions, it is about 25% to 70%. [0062] <<Cleaning method>> A cleaning method using the cleaning solution of the present invention is also one of the present invention. The cleaning method of the present invention is a method of cleaning a substrate by using the above-mentioned cleaning solution, an anti-corrosion agent, or a cleaning solution using the cleaning solution or anti-corrosion agent produced by the above-mentioned method to clean a substrate. [0064] The cleaning of the substrate is suitable as the cleaning of the substrate in photolithography. For example, in the cleaning method of the present embodiment, the etching mask layer forming step of forming an etching mask layer of a specific pattern on the surface of the substrate is performed after the etching step of etching the substrate exposed from the etching mask layer, A method of cleaning the etched substrate described above. The cleaning method of the present embodiment is suitable when at least a part of the surface of the substrate is made of silicide or other corrosive metals such as cobalt, copper, tungsten, and SiGe. At this time, although at least a part of silicides such as cobalt, copper, tungsten, SiGe, and other corrosive metals are exposed on the surface of the substrate, and contact with the cleaning solution, the silicides such as cobalt, copper, tungsten, and SiGe are other Corrosion of corrosive metals is well suppressed. Therefore, by cleaning with the above cleaning solution, the object to be cleaned can be effectively removed while suppressing corrosion of silicides such as cobalt, copper, tungsten, SiGe and other corrosive metals. As will be described later, the cleaning method of the present embodiment is as small as 0.2 nm/min or less, preferably 0.1 nm/min or less, more preferably 0.09 nm/min or less with respect to cobalt, based on the evaluation of the etching rate, Corrosion inhibition effect is large. Also, similarly, according to the evaluation of the etching rate, it can be as small as 0.4 nm/min or less, preferably 0.2 nm/min or less, more preferably 0.04 nm/min or less with respect to copper, and a corrosion inhibiting effect can be expected. Similarly, according to the evaluation of the etching rate, it can be as small as 0.2 nm/min or less, preferably 0.1 nm/min or less, and more preferably 0.01 nm/min or less with respect to tungsten, and a corrosion inhibiting effect can be expected. Also, similarly, according to the evaluation of the etching rate, it can be as small as 0.05 nm/min or less, preferably 0.01 nm/min or less with respect to SiGe, and a corrosion inhibiting effect can be expected. When the above-mentioned dialkanolamines and dialkanolamines are used, not only cobalt but also silicides such as copper, tungsten, SiGe and other corrosive metals such as copper, tungsten and SiGe can easily obtain a corrosion inhibitory effect. [0066] The specific cleaning method is not particularly limited if it is a method commonly performed. For example, a dipping method, a paddle method, a shower method, etc. are used to treat the substrate by contacting the substrate with the above-mentioned cleaning solution for 1 to 40 minutes. Although the cleaning is usually performed at room temperature, in order to improve the cleaning effect, the cleaning solution may be heated to about 85°C. <<Anti-corrosion method>> In this way, a method for preventing corrosion of corrosive metals by using the above-mentioned cleaning solution, anti-corrosion agent, or the cleaning solution or anti-corrosion agent produced by the above-mentioned method is also one of the present inventions. . The anti-corrosion method includes, for example, contacting silicides of cobalt, copper, tungsten, SiGe and other corrosive metals (such as a substrate with the corrosive metal exposed on the surface) with the cleaning solution or anti-corrosion agent, specifically It can be performed in the same manner as the cleaning method described above. Also, using the above-mentioned anti-corrosion agent or the anti-corrosion agent produced by the above-mentioned method, the method for preventing corrosion of corrosive metals, comprises adding the anti-corrosion agent to a cleaning solution, a developing solution, and a rinsing solution. , stripping solution and other lithography chemicals, etc., including the lithography chemicals, such as cobalt, copper, tungsten, SiGe and other silicides and other corrosive metals (such as the substrate with the corrosive metal exposed on the surface) and The lithography is contacted with a liquid. The anti-corrosion method is, for example, according to the type and application of the lithography chemical solution including the anti-corrosion agent, such as a cleaning solution, a developer, a rinsing solution, a stripping solution, etc., a cleaning method commonly used in photolithography can be used ( For example, the above-mentioned cleaning method), developing method, rinsing method, and peeling method. As the chemical solution for photolithography containing the anti-corrosion agent of the present embodiment, a cleaning solution and a developing solution are preferable. As this developer, for example, an alkali developer such as a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) can be used. [0069] The lithography liquid containing the anti-corrosion agent of the present invention is also one of the present invention. Examples of the chemical solution for lithography include a cleaning solution, a developing solution, a rinsing solution, and a stripping solution, and a cleaning solution is preferred. <<Method for manufacturing semiconductor>> A method for manufacturing a semiconductor including using the cleaning method of the present invention is also one of the present invention. The method for producing the semiconductor of the present invention includes a method for producing a semiconductor including a substrate by cleaning a substrate using the cleaning method described above. According to the method of this embodiment, as described above, when at least a part of the surface of the substrate is composed of silicides such as cobalt, copper, tungsten, SiGe and other corrosive metals, cobalt, copper, Corrosion of silicides such as tungsten, SiGe and other corrosive metals to manufacture semiconductors. <<Photolithography method>> A lithography method including the cleaning method of the present invention or the anticorrosion method of the present invention is also one of the present invention. The anti-corrosion method of the present invention may be a method of preventing corrosion of corrosive metals using the above-mentioned cleaning solution, anti-corrosion agent, or the cleaning solution or anti-corrosion agent produced by the above-mentioned method, or may include the anti-corrosion agent. The lithography chemical solution contained in the cleaning solution, developer solution, rinsing solution, stripping solution, etc., the above-mentioned anti-corrosion metal (such as the substrate with the corrosive metal exposed on the surface) is contacted with the lithography chemical solution. Corrosion method. [Examples] [0073] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. [Comparative Example] As a comparative example, a solution consisting of 75.0% by mass of ethyldiglycol, 2.0% by mass of tetramethylammonium hydroxide (TMAH), and 23.0% by mass of water (the remainder) was prepared. [Examples 1 to 4] In the examples, in the amounts shown in Table 1, alkanolamines (monoethanolamine, diethanolamine, monoisopropanolamine, and diisopropanolamine) were dissolved in water, respectively. Hydrogen peroxide water (H 2 O 2 ) was dropped over 60 minutes with stirring at 60°C. And after further reacting at 60 degreeC for 1 hour, the obtained reaction liquid was added so that it might become 0.5 mass part each with respect to 99.5 mass parts of the solutions used as a control example, and the washing|cleaning liquid was prepared. For example, the composition of the cleaning solution in Example 1 is 75.0 parts by mass of ethyl diethylene glycol, 2.0 parts by mass of tetramethylammonium hydroxide (TMAH), 0.5 parts by mass of the above-mentioned reaction solution and water (the remainder) 22.5 parts by mass. In embodiment 1～4, add the reaction solution of hydrogen peroxide water gained in alkanolamine, be as shown in table 3, be the mixture of the alkanolamine of starting material, and the alkanol hydroxylamine of the product of oxidation reaction All of them were confirmed by liquid chromatography mass spectrometry (LC-MS). [0078] An example of the analysis results is shown. In the reaction solution obtained in Example 4, as a result of evaluation by liquid chromatography mass spectrometry (LC-MS), peaks were observed at positions where m/z values were 134.1172 and 150.1122. From these results, it was found that the reaction solution obtained in Example 4 was a mixture of diisopropanolamine, which is a starting material, and diisopropanolhydroxylamine, which was a product of the oxidation reaction, and one hydroxyl group was bonded to a nitrogen atom. Moreover, as a result of evaluating the reaction solution of Example 4 by a nuclear magnetic resonance apparatus (NMR), it was confirmed that the molar ratio of starting material:reaction product=59:41, and the yield of diisopropanolhydroxylamine was 32.2%. [Example 5] As a cleaning solution, 1.0 mass % was added with respect to 100 mass % of an aqueous solution of tetramethylammonium hydroxide (TMAH) 2.38% (trade name: NMD-3, manufactured by Tokyo Oka Industry Co., Ltd.). % of the reaction solution obtained in Example 4 to prepare a cleaning solution. [Example 6] As a cleaning solution, based on 100 mass of an aqueous solution (trade name: NMD-W, manufactured by Tokyo Oka Industry Co., Ltd.) containing 2.38% of tetramethylammonium hydroxide (TMAH) and a surfactant %, and 1.0 mass % was added to the reaction solution obtained in Example 4 to prepare a cleaning solution. [Example 7] As a cleaning solution, 65% by mass of dipropylene glycol monomethyl ether (DPM), 5% by mass of propylene glycol (PG), 2.0% by mass of tetramethylammonium hydroxide (TMAH) and water (Remainder) 28 mass % of mixed solutions were added to the reaction solution obtained in Example 4 at 1.0 mass % to prepare a cleaning solution. [Comparative Examples 1 to 6] In Comparative Examples 1 to 6, as shown in Table 2, as the comparative compounds of the anticorrosion agent, monoethanolamine, diethanolamine, diethylamine, monoisopropanolamine, Each 0.5 mass part of the mixture obtained by diisopropanolamine, dipropylamine, and water was added with respect to 99.5 mass parts of solutions used as a control example, and the washing|cleaning liquid was prepared. [Comparative Example 7] In Comparative Example 7, in the amount shown in Table 1, as a comparative control compound of the anti-corrosion agent, hydrogen peroxide water (H 2 O 2 ) was dissolved in water with respect to dipropylamine. It was dripped over 60 minutes while stirring at 60 degreeC. And after further reacting at 60 degreeC for 1 hour, the obtained reaction liquid was added so that it might become 0.5 mass part with respect to 99.5 mass parts of the solutions used as a control example, and the washing|cleaning liquid was prepared. As shown in Table 4, the reaction liquid obtained in Comparative Example 7 is a mixture of dipropylamine and dipropylhydroxylamine. [Comparative Example 8] A cleaning solution was prepared in the same manner as in Example 5, except that it was not added to the reaction solution obtained in Example 4. [Comparative Example 9] A cleaning solution was prepared in the same manner as in Example 6, except that it was not added to the reaction solution obtained in Example 4. [Comparative Example 10] A cleaning solution was prepared in the same manner as in Example 7, except that it was not added to the reaction solution obtained in Example 4. [0087] [0088] [Evaluation of etching rate relative to copper layer, tungsten layer or cobalt layer] Copper, tungsten or cobalt was deposited on a silicon substrate to obtain a silicon substrate having a copper layer, tungsten layer or cobalt layer with a thickness of 100 nm. The silicon substrate was immersed in a cleaning solution heated to 60° C. for 60 minutes. After the immersion, the silicon substrate was rinsed with pure water, the film thickness of the copper layer, tungsten layer or cobalt layer was measured, and the etching rate of the copper layer, tungsten layer or cobalt layer was obtained from the difference in film thickness before and after immersion. The results are shown in Tables 3 and 4. [0090] The evaluation of the etching rates in Tables 3 and 4 is based on the following criteria. Furthermore, the etching rate obtained by the solution of the control example was 2.21 for the copper layer, 0.14 for the tungsten layer, and 0.35 for the cobalt layer. The unit of evaluation of the etching rate is [nm/min]. ‧Copper (Cu) ◎: 0.2 or less, ○: more than 0.2 and 0.4 or less, ×: more than 0.4 ‧Tungsten (W) ◎: 0.1 or less, ○: more than 0.1 and 0.2 or less, ×: more than 0.2 ‧Cobalt (Co ) ⊚: 0.1 or less, ○: more than 0.1 and 0.2 or less, ×: more than 0.2 [0091] [0092] From the results of Tables 3 and 4, the cleaning solutions of Examples 1 to 4 containing a mixed solution of alkanolhydroxylamine and alkanolamine, and the cleaning solutions of Comparative Examples 1 to 7 not containing alkanolhydroxylamine In comparison, the etching rate of cobalt is small and the corrosion inhibiting function is excellent. Among them, in the cleaning solutions of Examples 2 and 4 containing a mixed solution of dialkanolhydroxylamine and dialkanolamine, compared with the cleaning solutions of Comparative Examples 1 to 7, the etching rate of copper or tungsten was also lower, and corrosion was The inhibitory function is also excellent. In addition, it was confirmed that the alkanolhydroxylamines obtained in the examples all had larger LogP values, excellent water solubility, low vapor pressure, and excellent composition stability than the amines used in the comparative examples. [Evaluation of the etching rate of the SiGe layer] The silicon substrate having the SiGe layer with a thickness of 100 nm was immersed in the cleaning solutions (25° C.) of Examples 5 to 7 and Comparative Examples 8 to 10 for 10 minutes. After the immersion, the silicon substrate was rinsed with pure water, the film thickness of the SiGe layer was measured, and the etching rate of the SiGe layer was obtained from the difference between the film thicknesses before and after the immersion. The results are shown in Table 5. [0095] The evaluation of the etch rate in Table 5 is based on the following criteria. The unit of evaluation of the etching rate is [nm/min]. ‧SiGe ◎: 0.01 or less, ○: more than 0.01 and 0.05 or less, ×: more than 0.05 [0096] From the results in Table 5, the cleaning solutions of Examples 5 to 7 used in the reaction solution obtained in Example 4 containing the mixed solution of alkanolhydroxylamine and alkanolamine were different from those that did not contain alkanolhydroxylamine (1 , 1'(hydroxyimino)bis(2-propanol)), compared with the cleaning solutions of Comparative Examples 8 to 10, it was confirmed that the etching rate was small and the corrosion inhibition function was excellent even for the SiGe layer.