以下，對本發明之實施形態進行具體說明，但本發明並不限定於以下之實施形態，可於其主旨之範圍內進行各種變更而加以實施。 ＜半導體裝置用基板之清潔液＞ 本發明之半導體裝置用基板之清潔液(以下，有時稱為「本發明之清潔液」)係用於半導體裝置用基板之清潔，較佳為用於在半導體裝置製造中之CMP步驟之後進行之半導體裝置用基板之清潔步驟的清潔液，且pH為8以上且11.5以下，且含有以下之成分(A)～(E)。 成分(A)：含有選自由下述通式(1)～(3)所表示之化合物所組成之群中之至少1種的化合物 [化6]於上述通式(1)中，R1
～R6
分別獨立表示氫原子、碳數1～4之烷基、羧基、羰基或具有酯鍵之官能基。 [化7]於上述通式(2)中，R11
～R17
分別獨立表示氫原子、碳數1～4之烷基、羧基、羰基或具有酯鍵之官能基。 [化8]於上述通式(3)中，R21
～R28
分別獨立表示氫原子、碳數1～4之烷基、羧基、羰基或具有酯鍵之官能基。 成分(B)：抗壞血酸 成分(C)：多羧酸或羥基羧酸 成分(D)：pH調整劑 成分(E)：水 [組胺酸] 本發明之清潔液之組胺酸之含有率較佳為於清潔液總量100質量%中為0質量%以上且5質量%以下，更佳為0質量%以上且0.05質量%以下，進而較佳為0質量%以上且0.01質量%以下。 使用本發明之清潔液對半導體裝置用基板進行清潔時，該清潔液中之組胺酸之含有率較少者更佳，若為0.01質量%以下，則可大幅抑制組胺酸之影響。 又，本發明之清潔液若組胺酸之含有率於清潔液總量100質量%中為0質量%以上且0.01質量%以下，則即便用於CMP步驟後之半導體裝置用基板之清潔，亦不易形成微小異物。作為其原因，推測出以下之情況。 推測出若將包含組胺酸之清潔液用於CMP步驟後之半導體裝置用基板之清潔，則因某些原因，組胺酸與基板表面上之銅穩固地結合，而殘留於基板上之露出之銅表面。並且，推測出其結果為，成為如由組胺酸覆蓋於半導體裝置用基板上露出之銅之表面般之形式，大氣中之氧不易與基板上之銅結合。 原本係大氣中之氧與基板表面上之銅結合，可形成適當之厚度之氧化覆膜，但推測出若存在固定量以上之組胺酸，則因如上所述之原因，難以形成應形成於半導體裝置用之基板表面上之銅露出部分之氧化膜(CuO或Cu2
O)，假設即便形成，該氧化膜亦成為較薄者。 另一方面，若利用組胺酸之含有率於清潔液總量100質量%中為0質量%以上且0.01質量%以下之清潔液對半導體裝置用基板進行清潔，則易於形成銅之氧化膜，即便於清潔後在大氣下保管半導體裝置用基板，基板表面上之銅露出部分亦不會明顯氧化。作為結果，可抑制微小異物之形成。 根據上述推定機制，推察出將清潔後之半導體裝置用基板放置於大氣環境時發生異常氧化之原因在於：作為清潔液之成分而存在之固定量之組胺酸阻礙氧化覆膜之形成。 [pH] 本發明之清潔液之pH為8以上且11.5以下。藉由清潔液之pH為8以上，可使液中之膠體氧化矽等之ζ電位下降，使與基板之電性斥力作用。藉此，可容易地去除微小粒子，且可抑制去除之微小粒子再附著於清潔對象即基板表面。 此處，為了使ζ電位進一步下降，本發明之清潔液較佳為pH為9以上，進而較佳為pH為10以上。使pH變得越高，由於利用氧化膜保護Cu表面，故而越不易被蝕刻。 又，為了一面擔保清潔性，一面抑制腐蝕，而pH必須為11.5以下，較佳為11.3以下，更佳為11以下。 再者，本發明之清潔液中之pH可藉由下述成分(D)：pH調整劑或其他成分之添加量等調整為上述pH之範圍。 以下，關於本發明之清潔液中所包含之各成分與其作用一同進行詳細說明。 [成分(A)] 本發明之清潔液中所包含之成分(A)如上所述，係含有選自由上述通式(1)～(3)所表示之化合物所組成之群中之至少1種的化合物。 上述通式(1)～(3)所表示之化合物係於分子內具有2個胺基之化合物，該等化合物作為半導體裝置用基板之清潔液係發揮作為螯合劑之功能。具體而言，係具有藉由螯合作用將基板表面之金屬配線中所包含之鎢等雜質金屬、或於在CMP步驟中所使用之障壁漿料中存在之防蝕劑與銅之不溶性金屬錯合物、鈉或鉀等鹼金屬溶解、去除之作用者。 如上所述，於上述通式(1)中，R1
～R6
分別獨立表示氫原子、碳數1～4之烷基、羧基、羰基或具有酯鍵之官能基。 作為碳數1～4之烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基等。 較佳為R1
～R6
分別獨立表示氫原子或碳數1～4之烷基，更佳為R1
～R6
分別獨立表示氫原子、甲基或乙基，進而較佳為R1
～R6
分別獨立表示氫原子或甲基。 如上所述，於上述通式(2)中，R11
～R17
分別獨立表示氫原子、碳數1～4之烷基、羧基、羰基或具有酯鍵之官能基。 作為碳數1～4之烷基，與上述相同。 較佳為R1 1
～R17
分別獨立表示氫原子或碳數1～4之烷基，更佳為R1 1
～R17
分別獨立表示氫原子、甲基或乙基，進而較佳為R11
～R17
分別獨立表示氫原子或甲基。 如上所述，於上述通式(3)中，R21
～R28
分別獨立表示氫原子、碳數1～4之烷基、羧基、羰基或具有酯鍵之官能基。 作為碳數1～4之烷基，與上述相同。 較佳為R21
～R28
分別獨立表示氫原子或碳數1～4之烷基，更佳為R21
～R28
分別獨立表示氫原子、甲基或乙基，進而較佳為R21
～R28
分別獨立表示氫原子或甲基。 又，作為成分(A)，就有機殘渣去除之觀點而言，較佳為含有選自由上述通式(1)～(2)所表示之化合物所組成之群中之至少1種，更佳為含有上述通式(2)所表示之化合物。 成分(A)更佳為含有選自由1,2-二胺基乙烷、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、2-甲基-1,3-二胺基丙烷所組成之群中之至少1種，進而較佳為含有選自由1,2-二胺基丙烷、1,3-二胺基丙烷、N-甲基-1,3-二胺基丙烷所組成之群中之至少1種，尤佳為含有選自由1,3-二胺基丙烷、N-甲基-1,3-二胺基丙烷所組成之群中之至少1種。 成分(A)可單獨使用1種，亦可以任意之比率併用2種以上。 [成分(B)] 關於本發明之清潔液中所包含之成分(B)之抗壞血酸，作為較佳者可列舉：L-抗壞血酸、D-抗壞血酸、異抗壞血酸，又，亦可較佳地使用其等之鹽。進而較佳為使用L-抗壞血酸。抗壞血酸可使水溶液之氧化還原電位下降，抑制銅等金屬之氧化狀態。 [成分(C)] 本發明之清潔液中所包含之成分(C)為多羧酸或羥基羧酸。所謂多羧酸，係於分子內具有2個以上之羧基之化合物，所謂羥基羧酸，係於分子內具有1個以上之羥基及1個以上之羧基之化合物。 其等之中，較佳為於分子內具有2個以上之羧基及1個以上之羥基之化合物。 作為成分(C)，碳數相對較少之化合物更容易獲得或操作，因此，該化合物之碳數較佳為2～10，進而較佳為3～8，尤佳為3～6。 作為成分(C)之較佳之具體例，可列舉：草酸、檸檬酸、酒石酸、蘋果酸、乳酸，尤佳為檸檬酸。 其等可單獨使用1種，亦可以任意之比率併用2種以上。 又，亦可於不損害本發明之效果之範圍內，使用成分(C)之羧基之一部分成為鹽者。 [成分(D)] 本發明之清潔液之成分(D)之pH調整劑只要為可調整為其目標pH之成分，則並無特別限定，可使用酸性化合物或鹼性化合物。 關於酸性化合物，作為較佳之例，可列舉：硫酸或硝酸等無機酸及其鹽、或乙酸、乳酸、草酸、酒石酸、檸檬酸等有機酸及其鹽。再者，亦存在成分(D)係與成分(C)相同之化合物之情況。 又，關於鹼性化合物，可使用有機鹼性化合物及無機鹼性化合物，關於有機鹼性化合物，作為較佳之具體例，可列舉：以下所示之有機四級銨氫氧化物等四級銨及其衍生物之鹽、三甲胺、三乙胺等烷基胺及其衍生物之鹽、單乙醇胺等烷醇胺及其衍生物。 關於作為有機鹼性化合物之有機四級銨氫氧化物，可列舉下述通式(4)所表示者。(上述通式(4)中，R31
表示可由羥基、烷氧基或鹵素取代之烷基，4個R31
可彼此相同，亦可不同) 作為有機四級銨氫氧化物，較佳為於上述通式(4)中，R31
係可由羥基、碳數1～4之烷氧基、或鹵素取代之直鏈或支鏈之碳數1～4之烷基者。 作為上述烷基，尤佳為直鏈之碳數1～4之烷基及/或直鏈之碳數1～4之羥烷基。 作為碳數1～4之烷基，可列舉：甲基、乙基、丙基、丁基等。 作為碳數1～4之羥烷基，可列舉：羥甲基、羥乙基、羥丙基、羥丁基等。 作為該有機四級銨氫氧化物，具體可列舉：雙(2-羥乙基)二甲基氫氧化銨、四乙基氫氧化銨(TEAH)、四丙基氫氧化銨、四丁基氫氧化銨、甲基三乙基氫氧化銨、三甲基(羥乙基)氫氧化銨(通稱：膽鹼)、三乙基(羥乙基)氫氧化銨等。 上述有機四級銨氫氧化物之中，根據清潔效果、金屬之殘留較少，經濟性、清潔液之穩定性等理由，尤佳為雙(2-羥乙基)二甲基氫氧化銨、三甲基(羥乙基)氫氧化銨、四乙基氫氧化銨、四丁基氫氧化銨等。 無機鹼性化合物係於水溶液中表現出鹼性者中之氨或者主要包含鹼金屬或鹼土金屬之無機化合物及其鹽，其等之中，作為無機鹼性化合物，於安全性或成本之方面，較佳為使用包含鹼金屬之氫氧化物。具體可列舉：氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銣、氫氧化銫等。 該等酸性化合物或鹼性化合物於以調整本發明之清潔液之pH為目的而使用之情形時，可單獨使用1種，亦可以任意之比率併用2種以上。 作為尤佳之酸性化合物或鹼性化合物，可列舉：乙酸、草酸、酒石酸、檸檬酸等有機酸及其鹽、氫氧化鈉、氫氧化鉀等無機鹼性化合物及其鹽、四甲基氫氧化銨、四乙基氫氧化銨、膽鹼等四級銨及其衍生物之鹽。 [成分(E)] 作為本發明之清潔液之成分(E)之水係本發明之清潔液之溶劑。作為用作溶劑之水，較佳為使用儘量使雜質減少之去離子水或超純水。再者，本發明之清潔液亦可於不損害本發明之效果之範圍內包含乙醇等水以外之溶劑。 ＜清潔液之製造方法＞ 本發明之清潔液之製造方法並無特別限定，按照先前公知之方法即可，例如可藉由將清潔液之構成成分(成分(A)～(E)、視需要而使用之其他成分)混合而進行製造。通常，藉由向作為溶劑之成分(E)：水中添加成分(A)～(D)、視需要而使用之其他成分進行製造。 此時之混合順序亦只要不存在產生反應或沈澱物等特殊之問題，則為任意，可預先調配清潔液之構成成分中之任2種成分或3種成分以上，其後將其餘之成分混合，亦可一次性將所有成分混合。 [本發明之清潔液中之各成分之濃度] 本發明之清潔液中，成分(A)之濃度通常為0.001～20質量%，較佳為0.001～10質量%，更佳為0.001～0.80質量%，進而較佳為0.001～0.40質量%，尤佳為0.002～0.30質量%。 若本發明之清潔液中，成分(A)之濃度為0.001質量%以上，則充分發揮半導體裝置用基板之污染之去除效果，若為20質量%以下，則不易引起Cu等金屬配線之腐蝕等缺陷。 本發明之清潔液中，成分(B)之濃度通常為0.001～20質量%，較佳為0.001～10質量%，更佳為0.001～0.80質量%，進而較佳為0.005～0.40質量%，尤佳為0.01～0.30質量%。 若本發明之清潔液中，成分(B)之濃度為0.001質量%以上，則不易引起Cu等金屬配線之腐蝕等缺陷，若為20質量%以下，則不會過於耗費清潔液之成本。 本發明之清潔液中，成分(C)之濃度通常為0.001～10質量%，較佳為0.001～7質量%，更佳為0.001～0.40質量%，進而較佳為0.002～0.28質量%，尤佳為0.005～0.20質量%。 若本發明之清潔液中，成分(C)之濃度為0.001質量%以上，則充分發揮半導體裝置用基板之污染之去除效果，若為10質量%以下，則不會過於耗費清潔液之成本。 又，本發明之清潔液中，成分(D)係用於調整pH，因此，成分(D)之濃度並無特別限定，通常為0.002～30質量%，較佳為0.002～20質量%，更佳為0.002～1質量%，進而較佳為0.01～0.5質量%，尤佳為0.1～0.3質量%。 本發明之清潔液亦可以成為適於清潔之濃度之方式對各成分之濃度進行調整而製造，但就抑制輸送、保管時之成本之觀點而言，於製造以高濃度含有除成分(E)：水以外之各成分之清潔液(以下，有時稱為「清潔原液」)之後利用成分(E)：水進行稀釋而使用之情況亦較多。 成分(A)與成分(B)之質量比(成分(B)之質量/成分(A)之質量)就半導體裝置用基板之污染之去除性與Cu等金屬配線之腐蝕之抑制的觀點而言，較佳為0.01～100，更佳為0.1～25，尤佳為0.5～10。 成分(A)與成分(C)之質量比(成分(C)之質量/成分(A)之質量)就半導體裝置用基板之污染之去除性與Cu等金屬配線之腐蝕之抑制的觀點而言，較佳為0.1～200，更佳為0.5～50，尤佳為1～20。 成分(A)與成分(D)之質量比(成分(D)之質量/成分(A)之質量)就半導體裝置用基板之污染之去除性、Cu等金屬配線之腐蝕之抑制及pH之調整的觀點而言，較佳為0.05～500，更佳為0.1～200，尤佳為0.2～50。 成分(B)與成分(C)之質量比(成分(C)之質量/成分(B)之質量)就半導體裝置用基板之污染之去除性的觀點而言，較佳為0.25～20，更佳為0.5～10，尤佳為0.1～5。 成分(B)與成分(D)之質量比(成分(D)之質量/成分(B)之質量)就半導體裝置用基板之污染之去除性與pH之調整的觀點而言，較佳為0.1～100，更佳為0.5～50，尤佳為1～10。 成分(C)與成分(D)之質量比(成分(D)之質量/成分(C)之質量)就半導體裝置用基板之污染之去除性與pH之調整的觀點而言，較佳為0.1～100，更佳為0.5～50，尤佳為1～10。 [清潔原液中之各成分之濃度] 上述清潔原液中，成分(A)之濃度通常為0.10～20質量%，較佳為0.10～10質量%，更佳為0.20～7質量%。 上述清潔原液中，成分(B)之濃度通常為0.10～20質量%，較佳為0.50～10質量%，更佳為1.00～7質量%。 上述清潔原液中，成分(C)之濃度通常為0.10～10質量%，較佳為0.20～7質量%，更佳為0.50～5質量%。 上述清潔原液中，成分(D)之濃度通常為0.20～30質量%，較佳為0.50～20質量%，更佳為1.00～10質量%。 若上述清潔原液中之成分(A)～(D)之濃度處於此種範圍，則成分(A)～(D)及視需要而添加之其他成分以及其等之反應物於輸送、保管時，不易於清潔原液中分離或析出，又，藉由添加成分(E)：水，可較佳地用作容易適於清潔之濃度之清潔液。 再者，本發明之清潔液可以成為各成分之濃度對於成為清潔對象之半導體裝置用基板適當者之方式稀釋清潔原液而進行製造，亦可以成為該濃度之方式直接調整各成分而進行製造，但較佳為稀釋清潔原液而進行製造。 作為稀釋清潔原液而製造之本發明之清潔液之稀釋倍率係根據成為清潔對象之半導體裝置用基板而適當進行決定，但較佳為40～90倍。 再者，該清潔液中之上述成分(A)～(D)之各者之濃度係清潔原液中之上述成分(A)～(D)之各者之濃度除以稀釋倍率而得的值。 ＜半導體裝置用基板之清潔方法＞ 繼而，對本發明之半導體裝置用基板之清潔方法(以下，有時稱為「本發明之清潔方法」)進行說明。 本發明之清潔方法係藉由使上述本發明之清潔液直接接觸半導體裝置用基板之方法而進行。 作為成為清潔對象之半導體裝置用基板，可列舉：半導體、玻璃、金屬、陶瓷、樹脂、磁體、超導體等各種半導體裝置用基板。 該等之中，本發明之清潔液可藉由短時間之洗滌進行有機殘渣及研磨粒之去除，因此，尤佳用於作為配線等於表面具有金屬或金屬化合物之半導體裝置用基板，特別是較佳用於在表面具有Cu配線之半導體裝置用基板。 此處，作為用於半導體裝置用基板之上述金屬，可列舉：W、Cu、Ti、Cr、Co、Zr、Hf、Mo、Ru、Au、Pt、Ag等，作為用於半導體裝置用基板之上述金屬化合物，可列舉：上述金屬之氮化物、氧化物、矽化物等。 該等之中，將含有Cu及Cu之化合物更佳地用於半導體裝置用基板。 又，本發明之清潔方法即便針對疏水性較強之低介電常數絕緣材料，清潔效果亦較高，因此，亦較佳用於在表面具有低介電常數絕緣材料之半導體裝置用基板。 作為此種低介電常數絕緣材料，可列舉：聚醯亞胺(Polyimide)、BCB(Benzocyclobutene，苯并環丁烯)、Flare(商品名，Honeywell公司製造)、SiLK(商品名，Dow Chemical公司製造)等有機聚合物材料或FSG(Fluorinated silicate glass，氟矽酸鹽玻璃)等無機聚合物材料、BLACK DIAMOND(商品名，Applied Materials公司製造)、Aurora(商品名，日本ASM公司製造)等SiOC系材料。 此處，本發明之清潔方法尤佳地應用於半導體裝置用基板於基板表面具有Cu配線及低介電常數絕緣膜且於CMP處理後對基板進行清潔之情形。 於CMP步驟中，使用研磨劑於墊摩擦基板而進行研磨。 於研磨劑中包含膠體氧化矽(SiO2
)、薰製二氧化矽(SiO2
)、氧化鋁(Al2
O3
)、氧化鈰(CeO2
)等研磨粒子。此種研磨粒子成為半導體裝置用基板之微粒子污染之主要因素，但本發明之清潔液具有將附著於基板之微粒子去除並使其分散於清潔液中並且防止該微粒子之再附著的作用，因此對微粒子污染表現出較高之效果。 又，有於研磨劑中包含氧化劑、分散劑等研磨粒子以外之添加劑之情況。 尤其是於在其表面作為金屬配線而具有Cu膜之半導體裝置用基板中之CMP研磨中，由於Cu膜易腐蝕，因此添加防蝕劑之情況較多。 作為防蝕劑，較佳地使用防蝕效果較高之唑系防蝕劑。更具體而言，作為包含雜原子僅為氮原子之雜環者，可列舉：二唑系或三唑系、四唑系，作為包含雜原子為氮原子與氧原子之雜環者，可列舉：㗁唑系或異㗁唑系、㗁二唑系，作為包含雜原子為氮原子與硫原子之雜環者，可列舉：噻唑系或異噻唑系、噻二唑系。其中，尤佳地使用防蝕效果優異之苯并三唑(BTA)系防蝕劑。 本發明之清潔液若應用於利用此種包含防蝕劑之研磨劑進行研磨之後的基板表面，則於可儘量有效地去除來源於該等防蝕劑之污染之方面較為優異。 即，若於研磨劑中存在該等防蝕劑，則抑制Cu膜表面之腐蝕，另一面，與研磨時溶出之Cu離子發生反應，產生大量之不溶性析出物。本發明之清潔液可有效率地將此種不溶性析出物溶解去除，進而可藉由短時間之洗滌將易殘留於金屬表面之界面活性劑去除，實現產能之提高。 因此，本發明之清潔方法適於對Cu膜與低介電常數絕緣膜共存之表面進行CMP處理之後之半導體裝置用基板的清潔，尤其適於利用放入有唑系防蝕劑之研磨劑進行CMP處理後之上述基板之清潔。 如上所述，本發明之清潔方法係藉由使本發明之清潔液直接接觸半導體裝置用基板之方法而進行。再者，配合成為清潔對象之半導體裝置用基板之種類，選擇較佳之成分濃度的清潔液。 於本發明之清潔方法中之清潔液向基板之接觸方法中，可列舉：於清潔槽充滿清潔液使基板浸漬之浸漬式、一面使清潔液自噴嘴向基板上流入一面使基板高速旋轉之旋轉式、向基板噴霧液體之噴霧式等。作為用以進行此種清潔之裝置，有同時對收容於匣之複數片基板進行清潔之批次式清潔裝置、將1片基板安裝於保持器而進行清潔之單片式清潔裝置等。 本發明之清潔方法雖可應用上述任一種接觸方法，但就可於短時間更有效率地進行污染去除之方面而言，較佳宜使用旋轉式或噴霧式之清潔。於該情形時，若應用於期望清潔時間之縮短、清潔液使用量之消減之單片式清潔裝置，則該等問題得到解決，故而較佳。 又，本發明之清潔方法若併用利用物理力之清潔方法，尤其是使用清潔刷之刷洗清潔或頻率0.5兆赫以上之超音波清潔，則進一步提高因附著於基板之微粒子所造成之污染之去除性，亦關係到清潔時間之縮短，故而較佳。尤其是於CMP步驟後之清潔中，較佳為使用樹脂製刷進行刷洗清潔。樹脂製刷之材質可任意地進行選擇，例如較佳為PVA(polyvinyl alcohol，聚乙烯醇)。 進而，亦可於利用本發明之清潔方法之清潔之前及/或後進行利用水之清潔。 於本發明之清潔方法中，清潔液之溫度通常為室溫即可，但亦可於不損害性能之範圍內加溫至40～70℃左右。 ＜半導體裝置用基板＞ 本發明之半導體裝置用基板之製造方法包括使用本發明之清潔液對半導體裝置用基板進行清潔的步驟。 又，本發明之半導體裝置用基板係使用本發明之清潔液對半導體裝置用基板進行清潔而獲得者。 關於使用本發明之清潔液之半導體裝置用基板之清潔，如於＜半導體裝置用基板之清潔方法＞中所述。 [實施例] 以下，利用實施例對本發明更詳細地進行說明，但本發明只要不變更其主旨，則並不限定於以下之實施例。 [實施例1] ＜清潔液之製備＞ 如表1所示，將作為成分(A)之0.04質量%之1,3-二胺基丙烷(廣榮化學股份有限公司製造)、作為成分(B)之0.06質量%之抗壞血酸(扶桑化學工業股份有限公司製造)、作為成分(C)之0.09質量%之檸檬酸(昭和化工股份有限公司製造)、作為成分(D)之0.22質量%之四乙基氫氧化銨(TEAH：SACHEM日本有限公司製造)與成分(E)之超純水進行混合，從而製備半導體裝置用基板之清潔液。成分(E)之濃度設為除成分(A)、成分(B)、成分(C)、成分(D)、組胺酸及其他成分以外之剩餘濃度。 (pH測定) 對實施例1中所獲得之清潔液，一面使用磁力攪拌器進行攪拌，一面利用pH計(堀場製作所股份有限公司「D-24」)進行pH之測定。測定樣品係於恆溫槽中將液溫保持於25℃。將測定結果示於表1。 (缺陷評價) 使用成膜有Cu膜之矽基板之氧化矽漿料及CMP裝置(Lap Master SFT股份有限公司「LGP-15RD」)實施CMP。其後，一面將實施例1中所獲得之清潔液導入至基板表面，一面使用PVA之刷進行CMP步驟後之基板表面之清潔。 對清潔後之基板，使用晶圓表面檢查裝置(Hitachi High-Tech Fielding股份有限公司製造「LS-6600」)調查基板上之0.35 μm以上之缺陷數。將結果示於表1。 (有機物殘留評價、氧化膜厚評價) 於將在上述缺陷評價中使用之基板於大氣中放置90分鐘之後，利用X射線光電子光譜分析法(XPS)(PHI公司製造「Quantum 2000」)進行表面分析。以掠出角為45°、測定區域為300 μm進行測定。 來源於Cu2p3/2
之波峰係於932.5 eV檢測出，來源於N1s之波峰係於400 eV檢測出。對自各者之波峰強度檢測出之Cu與N之量進行測定，求出原子量比(N/Cu)。將結果示於表1。 若原子量比(N/Cu)較小，則表示殘留於Cu表面之含氮有機物量較少，因此，可認為CMP步驟後之基板表面上之有機殘渣較少。 該原子量比超過0.05時，殘留於Cu表面之含氮有機物量較多，因此，必須成為至少0.05以下，較佳為0.03以下。若該原子量比為0.05以下，則殘留於Cu表面之含氮有機物量較少，因此，CMP步驟後之基板表面上之有機殘渣較少。 又，來源於Cu氧化膜之波峰係於569 eV檢測出，來源於Cu金屬之波峰係於567 eV檢測出。求出569 eV與567 eV之強度比(569 eV/567 eV)。將結果示於表1。 該強度比未達0.9時，Cu氧化膜較薄，基板上所露出之銅表面之氧化於清潔後發生，因此，必須成為至少0.9以上，較佳為1.0以上。若該強度比為1.0以上，則銅表面之氧化得到抑制，因此，充分形成Cu氧化膜，可抑制基板表面上之微小異物之形成。 [實施例2] 於實施例1中，將成分(A)～(D)之調配比率設為表1所示者，除此以外，以同樣之方式獲得清潔液。 使用所獲得之清潔液，與實施例1同樣地進行pH測定、缺陷評價、有機物殘留評價、氧化膜厚評價。將結果示於表1。 [實施例3] 於實施例1中，將成分(A)設為1,2-二胺基丙烷(廣榮化學股份有限公司製造)，將成分(A)～(D)之調配比率設為表1所示者，除此以外，以同樣之方式獲得清潔液。 使用所獲得之清潔液，利用實施例1中記載之方法進行pH測定、缺陷評價、有機物殘留評價、氧化膜厚評價。將結果示於表1。 [實施例4] 於實施例1中，將成分(A)設為1,2-二胺基丙烷(廣榮化學股份有限公司製造)，將成分(A)～(D)之調配比率設為表1所示者，並加入0.04質量%之組胺酸(味之素股份有限公司製造)，除此以外，以同樣之方式獲得清潔液。 使用所獲得之清潔液，與實施例1同樣地進行pH測定、缺陷評價、有機物殘留評價、氧化膜厚評價。將結果示於表1。 [實施例5] 於實施例1中，將成分(A)設為1,2-二胺基丙烷(廣榮化學股份有限公司製造)，將成分(A)～(D)之調配比率設為表1所示者，並加入0.09質量%之組胺酸(味之素股份有限公司製造)，除此以外，以同樣之方式獲得清潔液。 使用所獲得之清潔液，與實施例1同樣地進行pH測定、缺陷評價、有機物殘留評價、氧化膜厚評價。將結果示於表1。 [實施例6] 於實施例1中，將成分(A)設為N-甲基-1,3-二胺基丙烷(廣榮化學股份有限公司製造)，將成分(A)～(D)之調配比率設為表1所示者，除此以外，以同樣之方式獲得清潔液。 使用所獲得之清潔液，與實施例1同樣地進行pH測定、缺陷評價、有機物殘留評價、氧化膜厚評價。將結果示於表1。 [比較例1] 於實施例1中，不使用成分(A)，將成分(B)～(D)之調配比率設為表1所示者，除此以外，以同樣之方式獲得清潔液。 使用所獲得之清潔液，與實施例1同樣地進行pH測定、缺陷評價、有機物殘留評價、氧化膜厚評價。將結果示於表1。 [比較例2] 於實施例1中，將成分(A)～(D)之調配比率設為表1所示者，除此以外，以同樣之方式獲得清潔液。 使用所獲得之清潔液，利用實施例1中記載之方法進行pH測定、缺陷評價。將結果示於表1。再者，於比較例2中，由於基板上之缺陷數較多，故而不進行有機物殘留評價、氧化膜厚評價。 [比較例3] 於實施例1中，使用N-(2-胺基乙基)哌𠯤(東京化成工業公司製造)來代替成分(A)，將N-(2-胺基乙基)哌𠯤及成分(B)～(D)之調配比率設為表1所示者，除此以外，以同樣之方式獲得清潔液。 使用所獲得之清潔液，利用實施例1中記載之方法進行pH測定、缺陷評價。將結果示於表1。再者，於比較例3中，由於基板上之缺陷數較多，故而不進行有機物殘留評價、氧化膜厚評價。 [比較例4] 於實施例1中，使用2-{[2-(二甲胺基)乙基]甲胺基}乙醇(東京化成工業公司製造)來代替成分(A)，將2-{[2-(二甲胺基)乙基]甲胺基}乙醇及成分(B)～(D)之調配比率設為表1所示者，除此以外，以同樣之方式獲得清潔液。 使用所獲得之清潔液，利用實施例1中記載之方法進行pH測定、缺陷評價。將結果示於表1。再者，於比較例4中，由於基板上之缺陷數較多，故而不進行有機物殘留評價、氧化膜厚評價。 [比較例5] 於實施例1中，使用N,N,N',N'-四(2-羥丙基)乙二胺(東京化成工業公司製造)來代替成分(A)，將N,N,N',N'-四(2-羥丙基)乙二胺及成分(B)～(D)之調配比率設為表1所示者，除此以外，以同樣之方式獲得清潔液。 使用所獲得之清潔液，利用實施例1中記載之方法進行pH測定、缺陷評價。將結果示於表1。再者，於比較例5中，由於基板上之缺陷數較多，故而不進行有機物殘留評價、氧化膜厚評價。 [表1]
實施例1係缺陷數少至5，原子量比(N/Cu)低至0.02，569 eV/567 eV下之波峰強度比亦成為1.0以上，因此可知，於Cu表面基本上不殘留含氮之化合物，又，Cu氧化膜形成得較厚，為於大氣中靜置時亦不易發生氧化之狀況。 實施例2、實施例3及實施例6亦相同。 實施例4及實施例5除了實施例1之成分以外，亦包含組胺酸，但是原子量比(N/Cu)雖稍高，但缺陷數較少。 另一方面，比較例1係原子量比(N/Cu)低至0.01，569 eV/567 eV下之波峰強度比亦高達1.4，不含有成分(A)，因此缺陷數多達55。 比較例2由於pH高達11.9，故而缺陷數較多。 比較例3～比較例5由於使用與上述通式(1)～(3)所表示之化合物不同之成分來代替成分(A)，故而缺陷數較多。 又，參照特定之實施態樣詳細地對本發明進行了說明，但對業者而言，明確可不脫離本發明之精神及範圍而添加各種變更或修正。本申請案係基於2017年3月22日提出申請之日本專利申請(日本專利特願2017-056371)及2017年11月1日提出申請之日本專利申請(日本專利特願2017-211495)者，其內容於本文中作為參照而引入。The embodiments of the present invention are specifically described below, but the present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention. <Cleaning liquid for substrate for semiconductor device> The cleaning liquid for a substrate for a semiconductor device of the present invention (hereinafter sometimes referred to as "cleaning liquid of the present invention") is used for cleaning a substrate for a semiconductor device, and is preferably used for cleaning The cleaning liquid for the cleaning step of the substrate for a semiconductor device which is performed after the CMP step in the manufacture of the semiconductor device has a pH of 8 or more and 11.5 or less, and contains the following components (A) to (E). Component (A): a compound containing at least one selected from the group consisting of compounds represented by the following general formulae (1) to (3) [Chemical Formula 6] In the above formula (1), R 1 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group or a functional group having an ester bond. [Chemistry 7] In the above formula (2), R 11 to R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group or a functional group having an ester bond. [化8] In the above formula (3), R 21 to R 28 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group or a functional group having an ester bond. Ingredient (B): Ascorbic acid component (C): polycarboxylic acid or hydroxycarboxylic acid component (D): pH adjuster component (E): water [histamine] The content of histidine in the cleaning liquid of the present invention is higher It is preferably 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 0.05% by mass or less, and further preferably 0% by mass or more and 0.01% by mass or less in 100% by mass of the total amount of the cleaning liquid. When the substrate for a semiconductor device is cleaned by using the cleaning liquid of the present invention, the content of histidine in the cleaning liquid is preferably smaller, and when it is 0.01% by mass or less, the influence of histidine can be greatly suppressed. In addition, when the content of histidine in the cleaning liquid of the present invention is 0% by mass or more and 0.01% by mass or less based on 100% by mass of the total amount of the cleaning liquid, even if the substrate for a semiconductor device is cleaned after the CMP step, It is not easy to form tiny foreign objects. The reason for this is presumed as follows. It is presumed that if the cleaning liquid containing histidine is used for the cleaning of the substrate for a semiconductor device after the CMP step, for some reason, histidine is firmly bonded to the copper on the surface of the substrate, and remains on the substrate. The copper surface. Further, it is presumed that the result is that the surface of the copper exposed on the substrate for the semiconductor device is covered with histidine, and the oxygen in the atmosphere is not easily bonded to the copper on the substrate. The oxygen in the atmosphere is combined with the copper on the surface of the substrate to form an oxide film of a suitable thickness. However, it is presumed that if a fixed amount or more of histidine is present, it is difficult to form it due to the above. The oxide film (CuO or Cu 2 O) of the exposed portion of the copper on the surface of the substrate for the semiconductor device is assumed to be thinner even if formed. On the other hand, when the substrate for a semiconductor device is cleaned by using a cleaning liquid having a content of histidine in a content of 0% by mass or more and 0.01% by mass or less based on 100% by mass of the total amount of the cleaning liquid, an oxide film of copper is easily formed. That is, the substrate for a semiconductor device is stored in the atmosphere after cleaning, and the exposed portion of the copper on the surface of the substrate is not significantly oxidized. As a result, the formation of minute foreign matter can be suppressed. According to the above-described estimation mechanism, it is found that the abnormal oxidation occurs when the cleaned semiconductor device substrate is placed in the atmosphere, and a fixed amount of histamine which is present as a component of the cleaning liquid hinders the formation of the oxide film. [pH] The pH of the cleaning liquid of the present invention is 8 or more and 11.5 or less. When the pH of the cleaning liquid is 8 or more, the zeta potential of the colloidal cerium oxide or the like in the liquid can be lowered to cause an electrical repulsion with the substrate. Thereby, the fine particles can be easily removed, and the removed fine particles can be prevented from adhering to the surface of the substrate to be cleaned. Here, in order to further lower the zeta potential, the cleaning liquid of the present invention preferably has a pH of 9 or more, and more preferably has a pH of 10 or more. The higher the pH is, the more difficult it is to be etched because the Cu surface is protected by the oxide film. Moreover, in order to ensure the cleanliness, the corrosion is suppressed, and the pH must be 11.5 or less, preferably 11.3 or less, more preferably 11 or less. Further, the pH in the cleaning liquid of the present invention can be adjusted to the above pH range by the following component (D): the amount of the pH adjusting agent or other components added, and the like. Hereinafter, each component contained in the cleaning liquid of the present invention will be described in detail together with its action. [Component (A)] The component (A) contained in the cleaning liquid of the present invention contains at least one selected from the group consisting of the compounds represented by the above formulas (1) to (3) as described above. compound of. The compound represented by the above formulas (1) to (3) is a compound having two amine groups in the molecule, and these compounds function as a chelating agent as a cleaning liquid system for a substrate for a semiconductor device. Specifically, it has an impurity metal such as tungsten contained in the metal wiring on the surface of the substrate by chelation, or an anti-corrosive agent present in the barrier paste used in the CMP step, which is incompatible with the insoluble metal of copper. The role of dissolution, removal of alkali metals such as substances, sodium or potassium. As described above, in the above formula (1), R 1 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group or a functional group having an ester bond. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, and a third butyl group. Preferably, R 1 to R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably R 1 to R 6 each independently represent a hydrogen atom, a methyl group or an ethyl group, and further preferably R 1 to R 6 independently represents a hydrogen atom or a methyl group. As described above, in the above formula (2), R 11 to R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group or a functional group having an ester bond. The alkyl group having 1 to 4 carbon atoms is the same as described above. Preferably, R 1 1 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably R 1 1 to R 17 each independently represent a hydrogen atom, a methyl group or an ethyl group, and further preferably R. 11 to R 17 each independently represent a hydrogen atom or a methyl group. As described above, in the above formula (3), R 21 to R 28 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group or a functional group having an ester bond. The alkyl group having 1 to 4 carbon atoms is the same as described above. Preferably, R 21 to R 28 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably R 21 to R 28 each independently represent a hydrogen atom, a methyl group or an ethyl group, and further preferably R 21 to R 28 independently represents a hydrogen atom or a methyl group. In addition, as the component (A), at least one selected from the group consisting of the compounds represented by the above formulas (1) to (2) is preferable, and more preferably The compound represented by the above formula (2) is contained. More preferably, the component (A) contains a compound selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2- At least one selected from the group consisting of methyl-1,3-diaminopropane, and more preferably contains one selected from the group consisting of 1,2-diaminopropane, 1,3-diaminopropane, and N-methyl. At least one selected from the group consisting of 1,3-diaminopropane, and more preferably contains at least one selected from the group consisting of 1,3-diaminopropane and N-methyl-1,3-diaminopropane. At least one of the groups. The component (A) may be used singly or in combination of two or more kinds in any ratio. [Component (B)] The ascorbic acid of the component (B) contained in the cleaning liquid of the present invention may, preferably, be L-ascorbic acid, D-ascorbic acid or isoascorbic acid, or may be preferably used. Wait for the salt. Further preferably, L-ascorbic acid is used. Ascorbic acid lowers the oxidation-reduction potential of the aqueous solution and suppresses the oxidation state of metals such as copper. [Component (C)] The component (C) contained in the cleaning liquid of the present invention is a polycarboxylic acid or a hydroxycarboxylic acid. The polycarboxylic acid is a compound having two or more carboxyl groups in the molecule, and the hydroxycarboxylic acid is a compound having one or more hydroxyl groups and one or more carboxyl groups in the molecule. Among them, a compound having two or more carboxyl groups and one or more hydroxyl groups in the molecule is preferable. As the component (C), a compound having a relatively small carbon number is more easily obtained or handled. Therefore, the carbon number of the compound is preferably from 2 to 10, more preferably from 3 to 8, particularly preferably from 3 to 6. Preferred examples of the component (C) include oxalic acid, citric acid, tartaric acid, malic acid, and lactic acid, and particularly preferably citric acid. These may be used alone or in combination of two or more kinds in any ratio. Further, a part of the carboxyl group of the component (C) may be used as a salt within a range not impairing the effects of the present invention. [Component (D)] The pH adjuster of the component (D) of the cleaning liquid of the present invention is not particularly limited as long as it is a component which can be adjusted to its target pH, and an acidic compound or a basic compound can be used. Preferred examples of the acidic compound include inorganic acids such as sulfuric acid or nitric acid and salts thereof, and organic acids such as acetic acid, lactic acid, oxalic acid, tartaric acid, and citric acid, and salts thereof. Further, there is also a case where the component (D) is the same compound as the component (C). Further, as the basic compound, an organic basic compound and an inorganic basic compound can be used. Specific examples of the organic basic compound include quaternary ammonium salts such as organic quaternary ammonium hydroxides and the like. a salt thereof, a salt of an alkylamine such as trimethylamine or triethylamine and a derivative thereof, an alkanolamine such as monoethanolamine, and a derivative thereof. The organic quaternary ammonium hydroxide which is an organic basic compound is represented by the following general formula (4). (In the above formula (4), R 31 represents an alkyl group which may be substituted by a hydroxyl group, an alkoxy group or a halogen, and four R 31 's may be the same as or different from each other) as the organic quaternary ammonium hydroxide, preferably In the above formula (4), R 31 may be a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms or a halogen. The alkyl group is preferably a linear alkyl group having 1 to 4 carbon atoms and/or a linear hydroxyalkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the hydroxyalkyl group having 1 to 4 carbon atoms include a methylol group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. Specific examples of the organic quaternary ammonium hydroxide include bis(2-hydroxyethyl)dimethylammonium hydroxide, tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, and tetrabutylhydrogen. Ammonium oxide, methyltriethylammonium hydroxide, trimethyl(hydroxyethyl)ammonium hydroxide (commonly known as: choline), triethyl(hydroxyethyl)ammonium hydroxide, and the like. Among the above organic quaternary ammonium hydroxides, bis(2-hydroxyethyl)dimethylammonium hydroxide is preferred because of the cleaning effect, the small amount of metal residues, the economy, the stability of the cleaning liquid, and the like. Trimethyl (hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and the like. The inorganic basic compound is an ammonia which exhibits basicity in an aqueous solution or an inorganic compound mainly containing an alkali metal or an alkaline earth metal, and a salt thereof, among which, as an inorganic basic compound, in terms of safety or cost, It is preferred to use a hydroxide containing an alkali metal. Specific examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and barium hydroxide. When the acidic compound or the basic compound is used for the purpose of adjusting the pH of the cleaning liquid of the present invention, one type may be used alone or two or more types may be used in any ratio. Examples of the acidic compound or basic compound which are particularly preferred include organic acids such as acetic acid, oxalic acid, tartaric acid, and citric acid, and salts thereof, inorganic basic compounds such as sodium hydroxide and potassium hydroxide, and salts thereof, and tetramethyl hydroxide. a salt of a quaternary ammonium such as ammonium, tetraethylammonium hydroxide or choline or a derivative thereof. [Component (E)] The water which is the component (E) of the cleaning liquid of the present invention is a solvent of the cleaning liquid of the present invention. As the water used as the solvent, it is preferred to use deionized water or ultrapure water which minimizes impurities. Further, the cleaning liquid of the present invention may contain a solvent other than water such as ethanol insofar as the effects of the present invention are not impaired. <Method for Producing Cleaning Liquid> The method for producing the cleaning liquid of the present invention is not particularly limited, and may be a conventionally known method. For example, the constituent components of the cleaning liquid (components (A) to (E), as needed The other components used are mixed and manufactured. Usually, it is produced by adding the components (A) to (D) to the component (E) as a solvent, and other components used as needed. In this case, the mixing order is arbitrary as long as there is no particular problem such as a reaction or a precipitate, and any two or more of the constituent components of the cleaning liquid may be prepared in advance, and then the remaining components may be mixed. You can also mix all the ingredients at once. [Concentration of each component in the cleaning liquid of the present invention] The concentration of the component (A) in the cleaning liquid of the present invention is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, more preferably 0.001 to 0.80 by mass. % is further preferably 0.001 to 0.40% by mass, particularly preferably 0.002 to 0.30% by mass. In the cleaning liquid of the present invention, when the concentration of the component (A) is 0.001% by mass or more, the effect of removing the contamination of the substrate for a semiconductor device is sufficiently exhibited, and if it is 20% by mass or less, corrosion of metal wiring such as Cu is less likely to occur. defect. In the cleaning liquid of the present invention, the concentration of the component (B) is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, more preferably 0.001 to 0.80% by mass, still more preferably 0.005 to 0.40% by mass, particularly Preferably, it is 0.01 to 0.30% by mass. When the concentration of the component (B) in the cleaning liquid of the present invention is 0.001% by mass or more, defects such as corrosion of metal wiring such as Cu are less likely to occur, and if it is 20% by mass or less, the cost of the cleaning liquid is not excessively consumed. In the cleaning liquid of the present invention, the concentration of the component (C) is usually 0.001 to 10% by mass, preferably 0.001 to 7% by mass, more preferably 0.001 to 0.40% by mass, still more preferably 0.002 to 0.28% by mass, particularly Preferably, it is 0.005 to 0.20% by mass. In the cleaning liquid of the present invention, when the concentration of the component (C) is 0.001% by mass or more, the effect of removing the contamination of the substrate for a semiconductor device is sufficiently exhibited, and if it is 10% by mass or less, the cost of the cleaning liquid is not excessively consumed. Further, in the cleaning liquid of the present invention, the component (D) is used for adjusting the pH. Therefore, the concentration of the component (D) is not particularly limited, but is usually 0.002 to 30% by mass, preferably 0.002 to 20% by mass, more preferably It is preferably 0.002 to 1% by mass, more preferably 0.01 to 0.5% by mass, still more preferably 0.1 to 0.3% by mass. The cleaning liquid of the present invention can be produced by adjusting the concentration of each component so as to be suitable for the concentration of the cleaning. However, from the viewpoint of suppressing the cost during transportation and storage, the cleaning component contains the component (E) at a high concentration. The cleaning liquid of each component other than water (hereinafter referred to as "cleaning stock solution") is often used after being diluted with the component (E): water. The mass ratio of the component (A) to the component (B) (the mass of the component (B) / the mass of the component (A)) is in view of the removal of the contamination of the substrate for a semiconductor device and the suppression of the corrosion of the metal wiring such as Cu. It is preferably from 0.01 to 100, more preferably from 0.1 to 25, still more preferably from 0.5 to 10. The mass ratio of the component (A) to the component (C) (the mass of the component (C) / the mass of the component (A)) is a viewpoint of the removal of the contamination of the substrate for a semiconductor device and the suppression of the corrosion of the metal wiring such as Cu. It is preferably from 0.1 to 200, more preferably from 0.5 to 50, still more preferably from 1 to 20. The mass ratio of the component (A) to the component (D) (the mass of the component (D) / the mass of the component (A)) the removal of the contamination of the substrate for the semiconductor device, the suppression of the corrosion of the metal wiring such as Cu, and the adjustment of the pH. From the viewpoint, it is preferably from 0.05 to 500, more preferably from 0.1 to 200, still more preferably from 0.2 to 50. The mass ratio of the component (B) to the component (C) (the mass of the component (C) / the mass of the component (B)) is preferably 0.25 to 20, from the viewpoint of the removal of the contamination of the substrate for a semiconductor device. Preferably, it is 0.5 to 10, and particularly preferably 0.1 to 5. The mass ratio of the component (B) to the component (D) (the mass of the component (D) / the mass of the component (B)) is preferably 0.1 in terms of the removal of the contamination of the substrate for a semiconductor device and the adjustment of the pH. ～100, more preferably 0.5 to 50, and particularly preferably 1 to 10. The mass ratio of the component (C) to the component (D) (the mass of the component (D) / the mass of the component (C)) is preferably 0.1 in terms of the removability of the contamination of the substrate for a semiconductor device and the adjustment of the pH. ～100, more preferably 0.5 to 50, and particularly preferably 1 to 10. [Concentration of each component in the cleaning stock solution] The concentration of the component (A) in the cleaning stock solution is usually 0.10 to 20% by mass, preferably 0.10 to 10% by mass, and more preferably 0.20 to 7% by mass. The concentration of the component (B) in the cleaning stock solution is usually 0.10 to 20% by mass, preferably 0.50 to 10% by mass, and more preferably 1.00 to 7% by mass. The concentration of the component (C) in the cleaning stock solution is usually 0.10 to 10% by mass, preferably 0.20 to 7% by mass, and more preferably 0.50 to 5% by mass. The concentration of the component (D) in the cleaning stock solution is usually 0.20 to 30% by mass, preferably 0.50 to 20% by mass, and more preferably 1.00 to 10% by mass. When the concentration of the components (A) to (D) in the cleaning stock solution is in such a range, the components (A) to (D) and other components to be added as needed, and the reactants thereof are transported and stored. It is not easy to clean the separation or precipitation in the stock solution, and by adding the component (E): water, it can be preferably used as a cleaning liquid which is easily suitable for cleaning. In addition, the cleaning liquid of the present invention may be produced by diluting the cleaning stock solution in such a manner that the concentration of each component is appropriate for the substrate for semiconductor device to be cleaned, and the components may be directly adjusted and manufactured by the concentration. It is preferably manufactured by diluting the cleaning stock solution. The dilution ratio of the cleaning liquid of the present invention produced by diluting the cleaning stock solution is appropriately determined depending on the substrate for the semiconductor device to be cleaned, but is preferably 40 to 90 times. Further, the concentration of each of the components (A) to (D) in the cleaning liquid is a value obtained by dividing the concentration of each of the components (A) to (D) in the cleaning stock solution by the dilution ratio. <Cleaning Method of Substrate for Semiconductor Device> Next, a method of cleaning a substrate for a semiconductor device of the present invention (hereinafter, referred to as "the cleaning method of the present invention") will be described. The cleaning method of the present invention is carried out by a method in which the cleaning liquid of the present invention is directly brought into contact with a substrate for a semiconductor device. Examples of the substrate for a semiconductor device to be cleaned include various semiconductor device substrates such as semiconductors, glass, metals, ceramics, resins, magnets, and superconductors. Among these, the cleaning liquid of the present invention can remove the organic residue and the abrasive particles by washing for a short period of time, and therefore, it is particularly preferably used as a substrate for a semiconductor device having a wiring equal to a metal or a metal compound on the surface, particularly It is preferably used for a substrate for a semiconductor device having Cu wiring on its surface. Here, examples of the metal used for the substrate for a semiconductor device include W, Cu, Ti, Cr, Co, Zr, Hf, Mo, Ru, Au, Pt, Ag, etc., and are used as substrates for semiconductor devices. Examples of the metal compound include nitrides, oxides, and tellurides of the above metals. Among these, a compound containing Cu and Cu is more preferably used for a substrate for a semiconductor device. Further, the cleaning method of the present invention is preferably used for a semiconductor device substrate having a low dielectric constant insulating material on its surface, even if it has a high cleaning effect against a low dielectric constant insulating material having high hydrophobicity. Examples of such a low dielectric constant insulating material include polyimide, BCB (Benzocyclobutene, benzocyclobutene), Flare (trade name, manufactured by Honeywell), and SiLK (trade name, Dow Chemical Co., Ltd.). Inorganic polymer materials such as FCL (Fluorinated silicate glass), BLACK DIAMOND (trade name, manufactured by Applied Materials), Aurora (trade name, manufactured by ASM Japan), etc. Department of materials. Here, the cleaning method of the present invention is particularly preferably applied to a substrate for a semiconductor device having a Cu wiring and a low dielectric constant insulating film on the surface of the substrate and cleaning the substrate after the CMP treatment. In the CMP step, the substrate is rubbed with a polishing agent to rub the substrate. Colloidal silicon oxide contained in the abrasive (SiO 2), silicon dioxide manufactured by Kaoru (SiO 2), alumina (Al 2 O 3), cerium oxide (CeO 2) abrasive particles and the like. Such a polishing particle is a major factor in the contamination of fine particles on a substrate for a semiconductor device. However, the cleaning liquid of the present invention has an effect of removing fine particles attached to the substrate and dispersing it in the cleaning liquid and preventing re-adhesion of the fine particles. Microparticle contamination shows a higher effect. Further, there are cases where an additive other than abrasive particles such as an oxidizing agent or a dispersing agent is contained in the polishing agent. In the CMP polishing in the substrate for a semiconductor device having a Cu film as a metal wiring on the surface thereof, since the Cu film is easily corroded, a corrosion inhibitor is often added. As the corrosion inhibitor, an azole-based corrosion inhibitor having a high corrosion resistance is preferably used. More specifically, examples of the heterocyclic ring containing a hetero atom and only a nitrogen atom include a diazole type, a triazole type, and a tetrazole type. Examples of the heterocyclic ring containing a nitrogen atom and an oxygen atom are mentioned. Examples of the oxazole-based or isoxazole-based or oxadiazole-based compounds include a thiazole-based or isothiazide-based or thiadiazole-based compound as a heterocyclic ring containing a nitrogen atom and a sulfur atom. Among them, a benzotriazole (BTA)-based corrosion inhibitor excellent in corrosion resistance is preferably used. When the cleaning liquid of the present invention is applied to the surface of the substrate after polishing using such an abrasive containing an anticorrosive agent, it is excellent in that contamination from the anticorrosive agent can be removed as efficiently as possible. That is, when such an anticorrosive agent is present in the polishing agent, corrosion of the surface of the Cu film is suppressed, and on the other hand, it reacts with Cu ions eluted during polishing to generate a large amount of insoluble precipitates. The cleaning liquid of the present invention can efficiently dissolve and remove such insoluble precipitates, and further removes the surfactant which is likely to remain on the metal surface by washing for a short period of time, thereby achieving an increase in productivity. Therefore, the cleaning method of the present invention is suitable for cleaning a substrate for a semiconductor device after CMP treatment of a surface in which a Cu film and a low dielectric constant insulating film are coexisted, and is particularly suitable for performing CMP using an abrasive containing an azole-based corrosion inhibitor. Cleaning of the above substrate after the treatment. As described above, the cleaning method of the present invention is carried out by directly contacting the cleaning liquid of the present invention with a substrate for a semiconductor device. Further, a cleaning liquid having a preferable component concentration is selected in accordance with the type of the substrate for semiconductor device to be cleaned. In the method for contacting the cleaning liquid to the substrate in the cleaning method of the present invention, the immersion type in which the cleaning tank is filled with the cleaning liquid to immerse the substrate, and the cleaning liquid is allowed to flow from the nozzle toward the substrate while rotating the substrate at a high speed. a spray method of spraying a liquid onto a substrate, or the like. As a device for performing such cleaning, there is a batch type cleaning device that simultaneously cleans a plurality of substrates accommodated in a crucible, a one-piece cleaning device that mounts one substrate to a holder and cleans it. Although the cleaning method of the present invention can be applied to any of the above contact methods, it is preferable to use a rotary or spray type cleaning in terms of more efficient removal of the contamination in a short period of time. In this case, if it is applied to a one-piece cleaning device in which the desired cleaning time is shortened and the amount of cleaning liquid used is reduced, such problems are solved, which is preferable. Moreover, the cleaning method of the present invention further improves the removal of the contamination caused by the microparticles attached to the substrate by using a cleaning method using physical force, in particular, cleaning with a cleaning brush or ultrasonic cleaning with a frequency of 0.5 MHz or more. It is also related to the shortening of the cleaning time, so it is better. Especially in the cleaning after the CMP step, it is preferred to use a resin brush for brush cleaning. The material of the resin brush can be arbitrarily selected, and for example, PVA (polyvinyl alcohol) is preferred. Further, cleaning with water may be performed before and/or after cleaning using the cleaning method of the present invention. In the cleaning method of the present invention, the temperature of the cleaning liquid is usually room temperature, but it may be heated to about 40 to 70 ° C within a range not impairing the performance. <Substrate for Semiconductor Device> The method for producing a substrate for a semiconductor device of the present invention includes a step of cleaning a substrate for a semiconductor device using the cleaning liquid of the present invention. Moreover, the substrate for a semiconductor device of the present invention is obtained by cleaning the substrate for a semiconductor device using the cleaning liquid of the present invention. The cleaning of the substrate for a semiconductor device using the cleaning liquid of the present invention is as described in <Method for Cleaning a Substrate for Semiconductor Devices>. EXAMPLES Hereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited to the following examples unless the scope of the invention is changed. [Example 1] <Preparation of cleaning liquid> As shown in Table 1, 0.04% by mass of 1,3-diaminopropane (manufactured by Kwong Wing Chemical Co., Ltd.) as component (A) was used as a component (B). 0.06质量% of ascorbic acid (manufactured by Fuso Chemical Industry Co., Ltd.), 0.09 mass% of citric acid (manufactured by Showa Chemical Co., Ltd.) as component (C), and 0.22% by mass of component (D) The ammonium hydroxide (TEAH: manufactured by SACHEM Japan Co., Ltd.) was mixed with the ultrapure water of the component (E) to prepare a cleaning liquid for the substrate for a semiconductor device. The concentration of the component (E) is a residual concentration other than the component (A), the component (B), the component (C), the component (D), histidine, and other components. (pH measurement) The pH of the cleaning liquid obtained in Example 1 was measured by a magnetic stirrer while using a pH meter ("D-24", Horiba, Ltd.). The sample was measured in a thermostat to maintain the liquid temperature at 25 °C. The measurement results are shown in Table 1. (Determination of Defects) CMP was carried out using a cerium oxide slurry and a CMP apparatus (Lap Master SFT Co., Ltd. "LGP-15RD") on which a Cu film was formed. Thereafter, the cleaning liquid obtained in Example 1 was introduced onto the surface of the substrate, and the surface of the substrate after the CMP step was cleaned using a PVA brush. For the cleaned substrate, a wafer surface inspection device ("LS-6600" manufactured by Hitachi High-Tech Fielding Co., Ltd.) was used to investigate the number of defects of 0.35 μm or more on the substrate. The results are shown in Table 1. (Evaluation of Organic Residues and Evaluation of Thickness of Oxide Film) After the substrate used for the above defect evaluation was left in the air for 90 minutes, surface analysis was performed by X-ray photoelectron spectroscopy (XPS) ("Quantum 2000" manufactured by PHI Corporation). . The measurement was carried out at a sweep angle of 45° and a measurement area of 300 μm. The peak derived from Cu2p 3/2 was detected at 932.5 eV, and the peak derived from N1s was detected at 400 eV. The amount of Cu and N detected from the peak intensity of each was measured, and the atomic weight ratio (N/Cu) was determined. The results are shown in Table 1. If the atomic weight ratio (N/Cu) is small, the amount of nitrogen-containing organic substances remaining on the Cu surface is small, and therefore, it is considered that the organic residue on the surface of the substrate after the CMP step is small. When the atomic weight ratio exceeds 0.05, the amount of the nitrogen-containing organic substance remaining on the Cu surface is large, and therefore it is necessary to be at least 0.05 or less, preferably 0.03 or less. When the atomic weight ratio is 0.05 or less, the amount of nitrogen-containing organic substances remaining on the Cu surface is small, and therefore, the organic residue on the surface of the substrate after the CMP step is small. Further, the peak derived from the Cu oxide film was detected at 569 eV, and the peak derived from Cu metal was detected at 567 eV. Find the intensity ratio of 569 eV to 567 eV (569 eV/567 eV). The results are shown in Table 1. When the intensity ratio is less than 0.9, the Cu oxide film is thin, and the oxidation of the copper surface exposed on the substrate occurs after cleaning. Therefore, it is necessary to be at least 0.9 or more, preferably 1.0 or more. When the intensity ratio is 1.0 or more, oxidation of the copper surface is suppressed. Therefore, the Cu oxide film is sufficiently formed, and formation of minute foreign matter on the surface of the substrate can be suppressed. [Example 2] In the first embodiment, the mixing ratio of the components (A) to (D) was set as shown in Table 1, except that the cleaning liquid was obtained in the same manner. Using the obtained cleaning liquid, pH measurement, defect evaluation, organic substance residue evaluation, and oxide film thickness evaluation were performed in the same manner as in Example 1. The results are shown in Table 1. [Example 3] In the first embodiment, the component (A) was used as 1,2-diaminopropane (manufactured by Kyoei Chemical Co., Ltd.), and the blending ratio of the components (A) to (D) was set to In addition to the above, the cleaning liquid was obtained in the same manner as shown in Table 1. Using the obtained cleaning liquid, pH measurement, defect evaluation, organic substance residue evaluation, and oxide film thickness evaluation were performed by the method of Example 1. The results are shown in Table 1. [Example 4] In the first embodiment, the component (A) was used as 1,2-diaminopropane (manufactured by Kyoei Chemical Co., Ltd.), and the blending ratio of the components (A) to (D) was set to The cleaning liquid was obtained in the same manner as in the above, except that 0.04% by mass of histamine (manufactured by Ajinomoto Co., Ltd.) was added. Using the obtained cleaning liquid, pH measurement, defect evaluation, organic substance residue evaluation, and oxide film thickness evaluation were performed in the same manner as in Example 1. The results are shown in Table 1. [Example 5] In the first embodiment, the component (A) was used as 1,2-diaminopropane (manufactured by Kyoei Chemical Co., Ltd.), and the blending ratio of the components (A) to (D) was set to The cleaning liquid was obtained in the same manner except that 0.09 mass% of histamine (manufactured by Ajinomoto Co., Ltd.) was added as shown in Table 1. Using the obtained cleaning liquid, pH measurement, defect evaluation, organic substance residue evaluation, and oxide film thickness evaluation were performed in the same manner as in Example 1. The results are shown in Table 1. [Example 6] In the first embodiment, the component (A) is N-methyl-1,3-diaminopropane (manufactured by Kwong Wing Chemical Co., Ltd.), and the components (A) to (D) are used. The mixing ratio was set as shown in Table 1, except that the cleaning liquid was obtained in the same manner. Using the obtained cleaning liquid, pH measurement, defect evaluation, organic substance residue evaluation, and oxide film thickness evaluation were performed in the same manner as in Example 1. The results are shown in Table 1. [Comparative Example 1] In the first embodiment, the cleaning liquid was obtained in the same manner except that the component (A) was not used, and the mixing ratio of the components (B) to (D) was as shown in Table 1. Using the obtained cleaning liquid, pH measurement, defect evaluation, organic substance residue evaluation, and oxide film thickness evaluation were performed in the same manner as in Example 1. The results are shown in Table 1. [Comparative Example 2] In the first embodiment, the mixing ratio of the components (A) to (D) was defined as shown in Table 1, except that the cleaning liquid was obtained in the same manner. Using the obtained cleaning liquid, pH measurement and defect evaluation were performed by the method described in Example 1. The results are shown in Table 1. Further, in Comparative Example 2, since the number of defects on the substrate was large, the evaluation of the organic substance residue and the evaluation of the oxide film thickness were not performed. [Comparative Example 3] In Example 1, N-(2-aminoethyl)piperazine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the component (A), and N-(2-aminoethyl)piperidin was used. The mixing ratio of the hydrazine and the components (B) to (D) was as shown in Table 1, except that the cleaning liquid was obtained in the same manner. Using the obtained cleaning liquid, pH measurement and defect evaluation were performed by the method described in Example 1. The results are shown in Table 1. Further, in Comparative Example 3, since the number of defects on the substrate was large, the evaluation of the organic substance residue and the evaluation of the oxide film thickness were not performed. [Comparative Example 4] In Example 1, 2-{[2-(dimethylamino)ethyl]methylamino}ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the component (A), and 2-{ The cleaning liquid was obtained in the same manner except that the mixing ratio of [2-(dimethylamino)ethyl]methylamino}ethanol and the components (B) to (D) was as shown in Table 1. Using the obtained cleaning liquid, pH measurement and defect evaluation were performed by the method described in Example 1. The results are shown in Table 1. Further, in Comparative Example 4, since the number of defects on the substrate was large, the evaluation of the organic substance residue and the evaluation of the oxide film thickness were not performed. [Comparative Example 5] In Example 1, N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the component (A), and N, The mixing ratio of N, N', N'-tetrakis(2-hydroxypropyl)ethylenediamine and the components (B) to (D) is as shown in Table 1, except that the cleaning liquid is obtained in the same manner. . Using the obtained cleaning liquid, pH measurement and defect evaluation were performed by the method described in Example 1. The results are shown in Table 1. Further, in Comparative Example 5, since the number of defects on the substrate was large, the evaluation of the organic substance residue and the evaluation of the oxide film thickness were not performed. [Table 1] In the first embodiment, the number of defects is as small as 5, the atomic weight ratio (N/Cu) is as low as 0.02, and the peak intensity ratio at 569 eV/567 eV is also 1.0 or more. Therefore, it is understood that substantially no nitrogen-containing compound remains on the Cu surface. Further, the Cu oxide film is formed thick, and is not easily oxidized when it is left standing in the atmosphere. The second embodiment, the third embodiment and the sixth embodiment are also the same. In addition to the components of Example 1, Example 4 and Example 5 also contained histidine, but the atomic weight ratio (N/Cu) was slightly higher, but the number of defects was small. On the other hand, in Comparative Example 1, the atomic weight ratio (N/Cu) was as low as 0.01, and the peak intensity ratio at 569 eV/567 eV was as high as 1.4, and the component (A) was not contained, so the number of defects was as high as 55. In Comparative Example 2, since the pH was as high as 11.9, the number of defects was large. In Comparative Examples 3 to 5, since the components different from the compounds represented by the above formulas (1) to (3) were used instead of the component (A), the number of defects was large. Further, the present invention has been described in detail with reference to the specific embodiments thereof, and it is obvious that various changes and modifications may be added without departing from the spirit and scope of the invention. The present application is based on a Japanese patent application filed on March 22, 2017 (Japanese Patent Application No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Its content is incorporated herein by reference.