JP4565741B2 - Silicate-containing alkaline composition for microelectronic substrate cleaning - Google Patents

Description

【００７１】
表１によれば、データはＴＭＡＳの、アルカリ溶液に曝されたことに伴うアルミ起伏の腐食を防ぐ能力を示し、珪酸テトラメチルアンモニウムを水酸化テトラメチルアンモニウムベースの洗浄溶液に添加することで、望ましくない集積回路の腐食が完全に阻害されることを示している。
【００７２】
実施例２
水溶液「Ｇ」は２．０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．１３重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１３．６である。水溶液「Ｈ」は０．０９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１０．８である。水溶液「Ｍ」は１．８重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および１．３重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１３．０である。水溶液「Ｎ」は１．９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．８６重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１３．２である。水溶液「Ｏ」は、１．９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．７０重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１３．２である。水溶液「Ｐ」は、１．９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．５４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１３．３である。水溶液「Ｑ」は、２．０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．４５重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１３．３である。水溶液「Ｒ」は、２．０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．２８重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１３．４である。水溶液「Ｓ」は、２．０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．１９重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１３．４である。水溶液「Ｔ」は、０．１重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．０２０重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１１．２である。水溶液「Ｕ」は、０．１重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．０７０重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１０．９である。（ａ）アルミ銅合金、次いで窒化チタンでメッキし、（ｂ）フォトレジスト材料を用いてリトグラフパターンをとり、（ｃ）反応性イオンエッチングを用いてパターンを転写し、（ｄ）酸素プラズマ灰化により有機フォトレジスト残渣を除去し、一方主に無機残渣を後に残すことで予め製造した、１ミクロン幅の起伏とアルミ銅で形成させ窒化チタンでキャップした配線とを有するウェーハー＃１サンプルを用いて溶液の性能を評価した。２１ないし６５℃にて５ないし２０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルを走査電子顕微鏡（ＳＥＭ）で観察してアルミ銅金属の起伏の洗浄および／または腐食の程度を求めた。結果を表２に示す。
【表２】

【００７３】
表２によれば、データはこれらのアルカリ溶液に曝されることに伴うアルミ起伏の腐食を防ぐ、または弱めるには、ｐＨが高まるにつれてＴＭＡＳ濃度を高める必要性があることを示し、本出願の溶液の至適ｐＨ範囲は約１１ないし１３であることを示している。
【００７４】
実施例３
水溶液「Ｉ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１３重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および５重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。水溶液「Ｊ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１３重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および６重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。水溶液「Ｋ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１２重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１０重量％ジエチレングリコール（ＤＥＧ）を加えて調製した。なお、この溶液の残部は水である。（ａ）アルミ銅合金、次いで窒化チタンでメッキし、（ｂ）フォトレジスト材料を用いてリトグラフパターンをとり、（ｃ）反応性イオンエッチングを用いてパターンを転写し、（ｄ）酸素プラズマ灰化により有機フォトレジスト残渣を除去し、一方主に無機残渣を後に残すことで予め製造した、１ミクロン幅の起伏とアルミ銅で形成させ窒化チタンでキャップした配線とを有するウェーハー＃１サンプルを用いて溶液の性能を評価した。２１ないし３５℃にて５ないし２０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルを走査電子顕微鏡（ＳＥＭ）で観察してアルミ銅金属の起伏の洗浄および／または腐食の程度を求めた。結果を表３に示す。
【表３】

【００７５】
表３によれば、データはＴＭＡＳ含有アルカリ溶液に曝されることに伴うアルミ起伏の腐食を防ぐ、または弱める能力には、水溶性有機溶媒の添加が有利であることを示し、本発明の組成物に水溶性溶媒を添加することで、集積回路に存在する金属配線の腐食を伴わずに洗浄時間を延長することが可能となることを示す。
【００７６】
実施例４
水溶液「Ｌ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および３重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。その基盤においてアルミ銅金属を露出する誘電材料を貫通する１ミクロンの深度の孔（バイアス）に対して１／２ミクロンの幅を有するウェーハーサンプル＃２は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機残渣を後に残すことで予め製造した。その基盤においてアルミ銅金属を露出する誘電材料を貫通する１ミクロンの深度のテーパー孔（バイアス）に対して１ミクロンの幅を有するウェーハーサンプル＃３は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機残渣を後に残すことで予め製造した。これらのサンプルを用いて溶液の性能を評価した。２０ないし２１℃にて１０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルの横断面をとり、次いで、走査電子顕微鏡（ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表４に示す。
【表４】

【００７７】
表４によれば、データはＴＭＡＳ含有アルカリ溶液に曝されることに伴うアルミ起伏の腐食を防ぐ、または弱める能力には、水溶性有機溶媒の添加が有利であることを示し、本発明の組成物に水溶性溶媒を添加することで、バイアスの基盤において金属の腐食を伴わずにバイアスの洗浄が可能となることを示す。
【００７８】
実施例５
（ａ）アルミ銅合金、次いで窒化チタンでメッキし、（ｂ）フォトレジスト材料を用いてリトグラフパターンをとり、（ｃ）反応性イオンエッチングを用いてパターンを転写し、（ｄ）酸素プラズマ灰化により有機フォトレジスト残渣を除去し、一方主に無機残渣を後に残すことで予め製造した、１ミクロン幅の起伏とアルミ銅で形成させ窒化チタンでキャップした配線とを有するウェーハー＃１および＃４サンプル各々を用いて溶液の性能を評価した。１１ないし６５℃にて５ないし３０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルを走査電子顕微鏡（ＳＥＭ）で観察してアルミ銅金属の起伏の洗浄および／または腐食の程度を求めた。結果を表５Ａ、５Ｂおよび５Ｃに示す。
【表５】

【表６】

【表７】

【００７９】
表５Ａ、５Ｂおよび５Ｃによれば、データは、水溶性有機溶媒を添加する（溶液「Ｌ」）か添加しない（溶液「Ａ」）、これら両配合にはかなりの加工寛容度があるということを示している。表５Ｂと５Ｃの比較もまた、水溶性有機溶媒の添加（溶液「Ｌ」）により、工程時間の延長および高温に伴って起こるアルミニウム金属腐食が減少し、加工寛容度がさらに改良されるということを示している。配合剤に有機溶媒を添加した表５Ｂでは、６５℃の洗浄温度を用いても、観察された腐食範囲はわずかに０ないし４％であった。有機溶媒を添加しなかった表５Ｃでは、１０分以上の洗浄時間で４％以上の腐食が観察された。データはまた、本発明の組成物を用いて得られるかなりの加工寛容度を示し、また所望による水溶性溶媒の添加によって加工寛容度をさらに改良できるということを示している。
【００８０】
実施例６
水溶液「Ｖ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である。水溶液「Ｗ」は０．６重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．３重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である。水溶液「Ｘ」は０．７重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である。（ａ）アルミ銅合金、次いで窒化チタンでメッキし、（ｂ）フォトレジスト材料を用いてリトグラフパターンをとり、（ｃ）反応性イオンエッチングを用いてパターンを転写し、（ｄ）酸素プラズマ灰化により有機フォトレジスト残渣を除去し、一方主に無機残渣を後に残すことで予め製造した、１ミクロン幅の起伏とアルミ銅で形成させ窒化チタンでキャップした配線とを有するウェーハー＃４サンプルを用いて溶液の性能を評価した。２０ないし２１℃にて５分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルを走査電子顕微鏡（ＳＥＭ）で観察してアルミ銅金属の起伏の洗浄および／または腐食の程度を求めた。結果を表６に示す。
【表８】

【００８１】
表６によれば、データは広範なＣｙＤＴＡ濃度にわたって良好なストリッピング性能が得られるということを示している。このように、存在するキレート剤の量を洗浄されるサンプルに適応するよう調節することができる。より難しいサンプルには、完全な洗浄を達成するためにこの所望による成分が必要となり得る。データはまた、本明細書に開示される組成物において所望によりキレート剤が使用されることを示している。
【００８２】
実施例７
水溶液「Ｙ」は０．４重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である。（ａ）アルミ銅合金、次いで窒化チタンでメッキし、（ｂ）フォトレジスト材料を用いてリトグラフパターンをとり、（ｃ）反応性イオンエッチングを用いてパターンを転写し、（ｄ）酸素プラズマ灰化により有機フォトレジスト残渣を除去し、一方主に無機残渣を後に残すことで予め製造した、１ミクロン幅の起伏とアルミ銅で形成させ窒化チタンでキャップした配線とを有するウェーハー＃４サンプルを用いて溶液の性能を評価した。２０ないし２１℃にて５分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルを走査電子顕微鏡（ＳＥＭ）で観察してアルミ銅金属の起伏の洗浄および／または腐食の程度を求めた。結果を表７に示す。
【表９】

【００８３】
表７によれば、データは基板の湿潤を改良するための界面活性剤を混合した処方に関して、良好なストリッピング性能が得られるということを示し、本明細書に開示される組成物において所望により界面活性剤が使用されることを示している。
【００８４】
実施例８
２種の異なる配合剤に対して標準的な槽を使用して開放槽経時変化実験を実施した。第１槽は室温で２４．７５時間作動させ、第２槽は４５℃で２４．７５時間作動させた。（ａ）アルミ銅合金、次いで窒化チタンでメッキし、（ｂ）フォトレジスト材料を用いてリトグラフパターンをとり、（ｃ）反応性イオンエッチングを用いてパターンを転写し、（ｄ）酸素プラズマ灰化により有機フォトレジスト残渣を除去し、一方主に無機残渣を後に残すことで予め製造した、１ミクロン幅の起伏とアルミ銅で形成させ窒化チタンでキャップした配線とを有するウェーハー＃４サンプルを用いて溶液の性能を評価した。２０℃または４５℃にて１０分間この槽にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルを走査電子顕微鏡（ＳＥＭ）で観察してアルミ銅金属の起伏の洗浄および／または腐食の程度を求めた。結果を表８に示す。
【表１０】

【００８５】
表８によれば、データは室温および高温での長期の開放槽経時変化の間の珪酸塩緩衝作用の利点を示している。この経時変化期間の間にストリッピング性能に変化は起こらなかった。データはまた、本発明の組成物は経時変化を受けないことを示している。
【００８６】
実施例９
水溶液「Ａ１」は０．２７重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）および０．１４重量％（ＳｉＯ₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ａ２」は０．３８重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９重量％キレート剤（エチレンジニトリロ）四酢酸（ＥＤＴＡ）および０．１４重量％（ＳｉＯ₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ａ３」は０．３９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１０重量％キレート剤ジエチレントリアミン五酢酸（ＤＥＴＰＡ）および０．１４重量％（ＳｉＯ₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ａ４」は０．４０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１０重量％キレート剤トリエチレンテトラミン六酢酸（ＴＴＨＡ）および０．１４重量％（ＳｉＯ₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ａ５」は、０．４０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１０重量％キレート剤１，３−ジアミノ−２−ヒドロキシプロパン−Ｎ，Ｎ，Ｎ’，Ｎ’−四酢酸（ＤＨＰＴＡ）および０．１４重量％（Ｓｉ０２％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ａ６」は、０．４７重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１３重量％キレート剤Ｎ，Ｎ，Ｎ’，Ｎ’−エチレンジアミンテトラ（メチレンホスホン酸）（ＥＤＴＭＰ）および０．１４重量％（ＳｉＯ₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。各溶液を１２５ｍｌガラス瓶に入れ、ゆるく蓋を締めて４５℃に設定したオーブンに１時間入れた。０．０５ｍｍ×１２ｍｍ×５０ｍｍ、９９．８％純度アルミ箔片をアセトンで洗浄し、乾燥させ、次いで化学天秤で秤量した。１時間予熱した後、各溶液をオーブンから取り出し、次いでアルミ箔片を瓶に入れ、再びゆるく蓋をしてオーブンに戻した。約４５℃で１時間後、瓶をオーブンから取り出した。アルミニウム片を取り出し、水洗し、次いでアセトンですすぎ、乾燥させてさらに化学天秤で秤量した。重量損失から相対的腐食度を求めた。結果を表９に示す。
【表１１】

【００８７】
表９によれば、データはアルミニウムエッチング速度を速めるには、キレート剤を添加が有用であることを示している。許容されるストリッピング温度および時間範囲における、酸素プラズマ灰化後のウェーハー上に見られる金属残渣の除去を可能にするには、アルミニウムエッチング速度を速める必要がある場合がある。データはまた、本明細書における発明の組成物に関して望ましいアルミニウムエッチング速度を得るためには、所望により様々な構造のキレート剤が使用されることを示している。
【００８８】
実施例１０
水溶液「Ｂ１」は０．２２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｂ２」は０．３０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｂ３」は０．４５重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．３０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．２）。水溶液「Ｂ４」は０．５９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．５０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．１）。水溶液「Ｂ５」は、１．１重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、１．０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｂ６」は、４．１重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、４．８重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）および０．１３重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。各溶液を１２５ｍｌポリエチレン瓶に入れ、ゆるく蓋を締めて４５℃に設定したオーブンに１時間入れた。０．０５ｍｍ×１２ｍｍ×５０ｍｍ、９９．８％純度アルミ箔片をアセトンすすぎ、乾燥させ、次いで化学天秤で秤量した。１時間予熱した後、各溶液をオーブンから取り出し、次いでアルミ箔片を瓶に入れ、再びゆるく蓋をしてオーブンに戻した。約４５℃にて１時間後、瓶をオーブンから取り出した。アルミニウム片を取り出し、水洗し、次いでアセトンですすぎ、乾燥させてさらに化学天秤で秤量した。重量損失から相対的腐食度を求めた。結果を表１０に示す。
【表１２】

【００８９】
表１０によれば、データはアルミニウムエッチング速度を速めるにはキレート剤の添加が有用であることを示している。許容されるストリッピング温度および時間範囲における、酸素プラズマ灰化後のウェーハー上に見られる金属残渣の除去を可能にするには、アルミニウムエッチング速度を速める必要がある場合がある。アルミニウムエッチング速度は使用されるキレート剤の量に正比例する。データはまた、本明細書における発明の組成物に関する所望のアルミニウムエッチング速度を得るためには、所望により種々の濃度で添加されるキレート剤が使用されることを示している。
【００９０】
実施例１１
水溶液「Ｃ１」は０．２５重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｃ２」は０．３６重量％コリンおよび０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｃ３」は０．７６重量％水酸化テトラブチルアンモニウム（ＴＢＡＨ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｃ４」は１．６重量％水酸化メチルトリエタノールアンモニウム（ＭＡＨ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｃ５」は、０．３６重量％水酸化メチルトリエチルアンモニウム（ＭＴＥＡＨ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。各溶液を１２５ｍｌガラス瓶に入れ、ゆるく蓋を締めて４５℃に設定したオーブンに１時間入れた。０．０５ｍｍ×１２ｍｍ×５０ｍｍ、９９．８％純度アルミ箔片をアセトンですすぎ、乾燥させ、次いで化学天秤で秤量した。１時間予熱した後、各溶液をオーブンから取り出し、次いでアルミ箔片を瓶に入れ、再びゆるく蓋をしてオーブンに戻した。約４５℃にて１時間後、瓶をオーブンから取り出した。アルミニウム片を取り出し、水洗し、次いでアセトンですすぎ、乾燥させてさらに化学天秤で秤量した。重量損失から相対的腐食度を求めた。結果を表１１に示す。
【表１３】

【００９１】
表１１によれば、データはアルミニウムエッチング速度を速めるには、ＴＭＡＨを種々の金属イオンフリー塩基で置き換えてもよいということを示している。許容されるストリッピング温度および時間範囲における、酸素プラズマ灰化後のウェーハーに見られる金属残渣の除去を可能にするには、アルミニウムエッチング速度を速める必要がある場合がある。データはまた、本明細書における発明の組成物に関して望ましいアルミニウムエッチング速度を得るためには、様々な構造の金属イオンフリーのアルカリ成分が使用されることを示している。
【００９２】
実施例１２
水溶液「Ｄ１」は０．１４重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｄ２」は０．２５重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｄ３」は１．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）および１．３重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．６）。水溶液「Ｄ４」は１．８重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）および２．８重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．６）。各溶液を１２５ｍｌガラス瓶に入れ、ゆるく蓋を締めて４５℃に設定したオーブンに１時間入れた。０．０５ｍｍ×１２ｍｍ×５０ｍｍ、９９．８％純度アルミ箔片をアセトンですすぎ、乾燥させ、次いで化学天秤で秤量した。１時間予熱した後、各溶液をオーブンから取り出し、次いでアルミ箔片を瓶に入れ、再びゆるく蓋をしてオーブンに戻した。約４５℃で１時間後、瓶をオーブンから取り出した。アルミニウム片を取り出し、水洗し、次いでアセトンですすぎ、乾燥させてさらに化学天秤で秤量した。重量損失から相対的腐食度を求めた。結果を表１２に示す。
【表１４】

【００９３】
表１２によれば、データは金属イオンフリー塩基性溶液に珪酸塩を添加することでアルミニウム金属の腐食が阻害されるということ示し、また本明細書における発明の組成物に関して望ましいアルミニウムエッチング速度を得るためには、種々の濃度で添加された金属イオンフリーの珪酸塩が使用されることを示している。
【００９４】
実施例１３
水溶液「Ｅ１」は０．２２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．２）。水溶液「Ｅ２」は０．２２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および２．９重量％グリセロールを加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．１）。水溶液「Ｅ３」は０．２０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１３重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および９．１重量％トリエチレングリコールモノメチルエーテルを加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．２）。水溶液「Ｅ４」は０．１９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１２重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１３重量％Ｎ−メチルピロリジノンを加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．２）。水溶液「Ｅ５」は、０．１９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１２重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１７重量％ジエチレングリコールを加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．１）。水溶液「Ｅ６」は、０．１７重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１１重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および２３重量％イソプロピルアルコールを加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．７）。各溶液を１２５ｍｌポリエチレン瓶に入れ、ゆるく蓋を締めて４５℃に設定したオーブンに１時間入れた。０．０５ｍｍ×１２ｍｍ×５０ｍｍ、９９．８％純度アルミ箔片をアセトンですすぎ、乾燥させ、次いで化学天秤で秤量した。１時間予熱した後、各溶液をオーブンから取り出し、次いでアルミ箔片を瓶に入れ、再びゆるく蓋をしてオーブンに戻した。約４５℃にて１時間後、瓶をオーブンから取り出した。アルミニウム片を取り出し、水洗し、次いでアセトンですすぎ、乾燥させてさらに化学天秤で秤量した。重量損失から相対的腐食度を求めた。結果を表１３に示す。
【表１５】

【００９５】
表１３によれば、データはアルミニウムエッチング速度を遅らせるためには、水溶性有機溶媒の添加が有用であることを示している。ストリッピング工程の間のアルミニウム腐食を完全に避けるには、アルミニウムエッチング速度を遅らせる必要がある場合がある。アルミニウムエッチング速度は、溶媒種類にかかわらず、使用される溶媒量に反比例する。広範な種類の水溶性溶媒が以下に示されている。データはまた、本明細書における発明の組成物に関して望ましいアルミニウムエッチング速度を得るためには、所望により種々のタイプの水溶性有機溶媒が使用されることを示している。
【００９６】
実施例１４
水溶液「Ｇ１」は０．２２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．２）。水溶液「Ｇ２」は０．２２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および０．１０重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．２）。水溶液「Ｇ３」は０．２２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および０．１０重量％非イオン界面活性剤Ｆｌｕｏｒａｄ ＦＣ−１７０Ｃ（3Mの工業用化学製品事業部の製品）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．２）。水溶液「Ｇ４」は０．２２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および０．０４２（有効）重量％両性界面活性剤Ｒｅｗｏｔｅｒｉｃ ＡＭ ＫＳＦ−４０（Witco Corporationの製品）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．２）。水溶液「Ｇ５」は、０．２２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および０．０２６（有効）重量％陰イオン界面活性剤Ｆｌｕｏｒａｄ ＦＣ−９３（3Mの工業用化学製品事業部の製品）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．２）。水溶液「Ｇ６」は、０．２２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および０．０３７（有効）重量％陽イオン界面活性剤Ｂａｒｑｕａｔ ＣＭＥ−３５（Lonza, Inc.の製品）を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．２）。各溶液を１２５ｍｌポリエチレン瓶に入れ、ゆるく蓋を締めて４５℃に設定したオーブンに１時間入れた。０．０５ｍｍ×１２ｍｍ×５０ｍｍ、９９．８％純度アルミ箔片をアセトンですすぎ、乾燥させ、次いで化学天秤で秤量した。１時間予熱した後、各溶液をオーブンから取り出し、次いでアルミ箔片を瓶に入れ、再びゆるく蓋をしてオーブンに戻した。約４５℃にて１時間後、瓶をオーブンから取り出した。アルミニウム片を取り出し、水洗し、次いでアセトンですすぎ、乾燥させてさらに化学天秤で秤量した。重量損失から相対的腐食度を求めた。結果を表１４に示す。
【表１６】

【００９７】
表１４によれば、データはアルミニウムエッチング速度を遅らせるには、界面活性剤の添加が有用であることを示している。ストリッピング工程の間のアルミニウム腐食を完全に避けるには、アルミニウムエッチング速度を遅らせる必要がある場合がある。有用なアルミニウムエッチング速度抑制は４種の界面活性剤すべてで起こる。このことは、界面活性剤が存在する場合のサンプルの湿潤性の向上という期待される望ましい特性に付加されるものである。データはまた、本明細書における発明の組成物に関して望ましいアルミニウムエッチング速度を得るためには、所望により種々のタイプの界面活性剤が使用されることを示している。
【００９８】
実施例１５
水溶液「Ｆ１」は０．２０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）および０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｆ２」は０．３０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．３）。水溶液「Ｆ３」は０．２９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）、３．０重量％グリセロールおよび０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を加えて調製した。なお、この溶液の残部は水である（溶液ｐＨ＝１２．１）。約６５０ｎｍの熱酸化物を有する同一のＳｉ（１００）ウェーハーからの切片をアセトンですすぎ、乾燥させ、次いでＲｕｄｏｌｐｈ ＦＴＭ干渉計を用いて測定して熱酸化物の厚みを求めた。４つの領域を測定し、処理後の追跡測定のためにマッピングした。次いで、各サンプルを瓶に入れ、再びゆるく蓋を締めて予め４５℃に設定したオーブンに入れた。約４５℃にて２４時間後、瓶をオーブンから取り出してサンプルを取り出し、水洗し、次いでアセトンですすぎ、乾燥させて、さらに干渉計で測定した。サンプル上の４つの領域について平均した熱酸化物フィルムの厚みの差異から相対的腐食度を求めた。結果を表１５に示す。
【表１７】

【００９９】
表１５によれば、データはアルカリ溶液に曝されることに伴う二酸化珪素の腐食を防ぐ、または弱めるには、珪酸塩の添加が有利であることを示している。通常、二酸化珪素誘電体は金属配線またはバイアスのストリッピングの間、集積回路表面に存在している。これらの誘電体に対する損傷は避けなければならない。データはまた、珪酸テトラメチルアンモニウムを水酸化テトラメチルアンモニウムベースの洗浄溶液に添加することで、通常、集積回路に存在する誘電材料の望ましくない腐食が阻害されることを示している。
【０１００】
実施例１６
二次イオン質量分析計（ＳＩＭＳ）を用いて洗浄後に残存する有機混入物を測定した。アルミ−１％銅合金の０．３５ミクロンフィルムでスパッターしたシリコーンウェーハーサンプルを珪酸塩溶液「Ａ」で、また市販のエッチング後残渣リムーバー、ＥＫＣ−２６５^TM（EKC Technology, Inc.の製品）でも洗浄した。ＥＫＣ−２６５^TMは約５％のカテコール、ヒドロキシルアミンと水を各々１５％ないし２０％含んでなり、残部は２−（２−アミノエトキシ）エタノールである。３５℃にて５分間溶液「Ａ」にウェーハーサンプルを入れ、次いで０．２ミクロンで濾過した脱イオン水で２分間すすいで加圧窒素乾燥させた。第２のウェーハーサンプルを、製造業者によって推奨される時間および温度を用いてＥＫＣ−２６５^TM中で同様に処理した。第３の未処理ウェーハー片（これもまた同一のシリコーンウェーハーからのもの）を対照として用いた。次いで、ウェーハーサンプルを、０．５秒の一時停止時間を伴う２２．１オングストローム／秒のエッチング速度を用いてＤｙｎａｍｉｃ−ＳＩＭＳによって解析した。次いで、表面から放出された炭素−１２の原子度数を用いてこの３種のサンプルの炭素表面汚染を比較した。結果を表１６に示す。
【表１８】

【０１０１】
表１６によれば、データは洗浄後に有機混入物のない表面を与えることに関する本発明の優位性を示し、本明細書に記載される組成物の使用により炭素含有（有機）不純物による集積回路の汚染がほとんどなくなるということを示す。
【０１０２】
実施例１７
水溶液「Ｈ１」は０．２７重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９２重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６２重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１３重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および２．７重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。水溶液「Ｈ２」は０．２８重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９７重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０６５重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１３重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および２．９重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。水溶液「Ｈ３」は０．３２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７５重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１５重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および３．３重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。水溶液「Ｈ４」は０．３９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１４重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０９１重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１９重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および４．０重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。水溶液「Ｈ５」は０．５８重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．２０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．２８重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および６．０重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。水溶液「Ｈ６」は１．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．２７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．５６重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１２重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。水溶液「Ｈ７」は５．１重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、１．８重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、２．４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および５２重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。（ａ）アルミ銅合金、次いで窒化チタンでメッキし、（ｂ）フォトレジスト材料を用いてリトグラフパターンをとり、（ｃ）反応性イオンエッチングを用いてパターンを転写し、（ｄ）酸素プラズマ灰化により有機フォトレジスト残渣を除去し、一方主に無機残渣を後に残すことで予め製造した、１ミクロン幅の起伏とアルミ銅で形成させ窒化チタンでキャップした配線とを有するウェーハー＃５および＃６サンプルを用いて溶液の性能を評価した。その基盤においてアルミ銅金属を露出する誘電材料を貫通する１ミクロンの深度の孔（バイアス）に対して１／２ミクロンの幅を有するウェーハーサンプル＃７および＃８は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機残渣を後に残すことで予め製造した。その基盤においてアルミ銅金属を露出する誘電材料を貫通する１ミクロンの深度のテーパー孔（バイアス）に対して１ミクロンの幅を有するウェーハーサンプル＃９は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機残渣を後に残すことで予め製造した。２１ないし４５℃にて５ないし１０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルを走査電子顕微鏡（ＳＥＭ）で観察してアルミ銅金属の起伏の洗浄および／または腐食の程度を求めた。結果を表１７Ａないし１７Ｅに示す。
【表１９】

【表２０】

【表２１】

【表２２】

【表２３】

【０１０３】
表１７Ａないし１７Ｅによれば、データはｐＨおよび各々の成分の濃度を変化させることで、７種の異なる配合で、許容されないアルミニウム腐食が起こらずに数種の異なる酸素プラズマ灰化したウェーハーサンプルから残渣を上手く洗浄することが可能となったことを示している。
【０１０４】
実施例１８
水溶液「Ｈ８」は５．１重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、１．８重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、２．４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および５２重量％ジメチルスルホキシド（ＤＭＳＯ）を加えて調製した。なお、この溶液の残部は水である。水溶液「Ｈ９」は０．５８重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．２０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．２８重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および６．０重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。水溶液「Ｈ１０」は０．８８重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．３０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．２０重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．４２重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および９．０重量％グリセロールを加えて調製した。なお、この溶液の残部は水である。その基盤においてフォトレジストおよびアルミ銅金属を露出する誘電材料を貫通する２ミクロンの深度の孔（バイアス）に対して１ミクロンの幅を有するウェーハーサンプル＃１０は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）約１ミクロンの厚みの層のフォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）高温でのフォトレジストの堅焼きにより溶媒を除去し、一方主に有機フォトレジスト層を後に残すことで予め製造した。このサンプルを用いて以下のように溶液の性能を評価した。４５ないし６５℃にて２０ないし３０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルを走査電子顕微鏡（ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表１８に示す。
【表２４】

【０１０５】
表１８によれば、データは本発明の、サンプルが酸素プラズマ灰化される前に半導体ウェーハー表面から有機フォトレジスト層を洗浄し、一方でアルミ起伏の腐食を防ぐ、または弱める能力を証明している。
【０１０６】
実施例１９
水溶液「Ｈ１１」は６．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、２．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、６４重量％グリセロールおよび２．９重量％（Ｓｉ０₂％換算）コロイド状シリカ溶液（２０ｎｍの粒子サイズを有する）を加えて調製した。なお、この溶液の残部は水である。溶液「Ｈ１１」のｐＨは約１３．１である。（ａ）アルミ銅合金、次いで窒化チタンでメッキし、（ｂ）フォトレジスト材料を用いてリトグラフパターンをとり、（ｃ）反応性イオンエッチングを用いてパターンを転写し、（ｄ）酸素プラズマ灰化により有機フォトレジスト残渣を除去し、一方主に無機残渣を後に残すことで予め製造した、１ミクロン幅の起伏とアルミ銅で形成させ窒化チタンでキャップした配線とを有するウェーハーサンプル＃５および＃６を用いた。各サンプルに対する処理を２２ないし４５℃にて５ないし１０分間行って取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルを走査電子顕微鏡（ＳＥＭ）で観察してアルミ銅金属の起伏の洗浄および／または腐食の程度を求めた。結果は実施例１７において溶液「Ｈ７」に関して得たものと同様であり、コロイド状シリカを本発明の水溶性の金属イオンを含まない珪酸塩の供給源として使用できるということを示している。
【０１０７】
実施例２０
水溶液「Ｌ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および３重量％グリセロールを加えて調製した。なお、この溶液の残部は水であり、このｐＨは約１２．１である。水溶液「Ｚ」は１．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．５８重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）を加えて調製し（この溶液の残部は水）、このｐＨは約１３．０である。水溶液「Ｍ１」は１．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）１８．５重量％ヒドロキシルアミンおよび０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｐ１」は２．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．６重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１１．５である。その基盤においてアルミ銅金属を露出する誘電層および窒化チタン層を貫通する０．５ミクロンの深度の孔（バイアス）に対して０．３ないし０．５ミクロンの幅を有するウェーハーサンプル＃１１は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機チタン含有残渣を後に残すことで予め製造した（残渣を経る横断面のＡｕｇｅｒ電子顕微鏡解析によって測定した）。これらのサンプルを用いて溶液の性能を評価した。２２ないし６５℃にて２０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルバイアスの横断面をとり、次いで電界放射走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表１９に示す。
【表２５】

【０１０８】
表１９によれば、データはヒドロキシルアミンまたは過酸化水素の、低温でのチタン含有残渣の除去を促進する能力を示している。
【０１０９】
実施例２１
水溶液「Ｍ２」は０．６７重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４６重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）、１．０重量％ヒドロキシルアミンおよび０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｍ３」は０．９４重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．２０重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）、５．１重量％ヒドロキシルアミンおよび０．１重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｍ４」は１．１重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４６重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１８重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）、１０．０重量％ヒドロキシルアミンおよび０．０９重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｍ５」は１．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４２重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および４７．３重量％ヒドロキシルアミンを用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。その基盤においてアルミ銅金属を露出する誘電層および窒化チタン層を貫通する０．５ミクロンの深度の孔（バイアス）に対して０．３ないし０．５ミクロンの幅を有するウェーハーサンプル＃１１は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機チタン含有残渣を後に残すことで予め製造した（残渣を経る横断面のＡｕｇｅｒ電子顕微鏡解析によって測定した）。これらのサンプルを用いて溶液の性能を評価した。３５℃にて２０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルバイアスの横断面をとり、次いで電界放射走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表２０に示す。
【表２６】

【０１１０】
表２０によれば、データはヒドロキシルアミンの低温でのチタン含有残渣の除去を促進する能力を示している。
【０１１１】
実施例２２
水溶液「Ｍ６」は０．８２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）、１８．８重量％ヒドロキシルアミンおよび０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。その基盤においてアルミ銅金属を露出する誘電層および窒化チタン層を貫通する０．５ミクロンの深度の孔（バイアス）に対して０．３ないし０．５ミクロンの幅を有するウェーハーサンプル＃１１は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機チタン含有残渣を後に残すことで予め製造した（残渣を経る横断面のＡｕｇｅｒ電子顕微鏡解析によって測定した）。これらのサンプルを用いて溶液の性能を評価した。３５℃にて２０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルバイアスの横断面をとり、次いで電界放射走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表２１に示す。
【表２７】

【０１１２】
表２１によれば、データはある範囲のＣｙＤＴＡ濃度にわたって良好なストリッピング性能が得られることを示す。従って、存在するキレート剤の量を洗浄されるサンプルに適応させるよう調節することができる。より難しいサンプルには、完全な洗浄を達成するためにこの所望による成分が必要となり得る。データはまた、本明細書に開示される組成物において所望によりキレート剤が使用されることを示している。
【０１１３】
実施例２３
水溶液「Ｍ７」は６．０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．３５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、１．２重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）、１７．７重量％ヒドロキシルアミンおよび０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１３．０である。水溶液「Ｍ８」は７．１重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４６重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、２．７重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１９．１重量％ヒドロキシルアミンを用いて調製し（この溶液の残部は水）、このｐＨは約１３．０である。水溶液「Ｍ９」は８．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、４．１重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１９．０重量％ヒドロキシルアミンを用いて調製し（この溶液の残部は水）、このｐＨは１３．０である。その基盤においてアルミ銅金属を露出する誘電層および窒化チタン層を貫通する０．５ミクロンの深度の孔（バイアス）に対して０．３ないし０．５ミクロンの幅を有するウェーハーサンプル＃１１は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機チタン含有残渣を後に残すことで予め製造した（残渣を経る横断面のＡｕｇｅｒ電子顕微鏡解析によって測定した）。これらのサンプルを用いて溶液の性能を評価した。３５℃にて２０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルバイアスの横断面をとり、次いで電界放射走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表２２に示す。
【表２８】

【０１１４】
表２２によれば、データは珪酸テトラメチルアンモニウムの、処方ｐＨが極めて高い場合でさえもバイアスの基盤における露出されたアルミニウムの腐食を防ぐ、または弱める能力を示している。
【０１１５】
実施例２４
水溶液「Ｍ１０」は０．３４重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４７重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０１重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）、１８．６重量％ヒドロキシルアミンおよび０．０６重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１０．１である。その基盤においてアルミ銅金属を露出する誘電層および窒化チタン層を貫通する０．５ミクロンの深度の孔（バイアス）に対して０．３ないし０．５ミクロンの幅を有するウェーハーサンプル＃１１は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機チタン含有残渣を後に残すことで予め製造した（残渣を経る横断面のＡｕｇｅｒ電子顕微鏡解析によって測定した）。これらのサンプルを用いて溶液の性能を評価した。２０ないし６５℃にて５ないし３０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルバイアスの横断面をとり、次いで電界放射走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表２３に示す。
【表２９】

【０１１６】
表２３によれば、データは高いｐＨ、高濃度の珪酸テトラメチルアンモニウムを用いてアルミニウム腐食を阻害することができることを示している。データはまた、高いｐＨ、低い作業温度も使用できるということを示している。
【０１１７】
実施例２５
水溶液「Ｐ１」は２．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．６重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１１．５である。水溶液「Ｐ２」は９．７重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および９．４重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１１．５である。その基盤においてアルミ銅金属を露出する誘電層および窒化チタン層を貫通する０．５ミクロンの深度の孔（バイアス）に対して０．３ないし０．５ミクロンの幅を有するウェーハーサンプル＃１１は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機チタン含有残渣を後に残すことで予め製造した（残渣を経る横断面のＡｕｇｅｒ電子顕微鏡解析によって測定した）。これらのサンプルを用いて溶液の性能を評価した。２１ないし３５℃にて２０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルバイアスの横断面をとり、次いで電界放射走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表２４に示す。
【表３０】

【０１１８】
表２４によれば、データはある範囲の過酸化水素濃度がバイアスにおけるチタン含有残渣の除去に有用であるということを示している。
【０１１９】
実施例２６
水溶液「Ｐ３」は３．５重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．５重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１２．２である。水溶液「Ｐ４」は３．９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０９６重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．５９重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．４重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１２．２である。その基盤においてアルミ銅金属を露出する誘電層および窒化チタン層を貫通する０．５ミクロンの深度の孔（バイアス）に対して０．３ないし０．５ミクロンの幅を有するウェーハーサンプル＃１１は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機チタン含有残渣を後に残すことで予め製造した（残渣を経る横断面のＡｕｇｅｒ電子顕微鏡解析によって測定した）。これらのサンプルを用いて溶液の性能を評価した。２２℃にて１０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルバイアスの横断面をとり、次いで電界放射走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表２５に示す。
【表３１】

【０１２０】
表２５によれば、データは過酸化水素が存在する場合には高濃度の珪酸テトラメチルアンモニウムを用いてアルミニウム腐食を阻害することができるということを示している。
【０１２１】
実施例２７
水溶液「Ｐ５」は２．１重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．５重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１１．５である。水溶液「Ｐ６」は２．４重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．５３重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．６重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１１．５である。水溶液「Ｐ７」は２．９重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、１．４重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．５重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１１．５である。その基盤においてアルミ銅金属を露出する誘電層および窒化チタン層を貫通する０．５ミクロンの深度の孔（バイアス）に対して０．３ないし０．５ミクロンの幅を有するウェーハーサンプル＃１１は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機チタン含有残渣を後に残すことで予め製造した（残渣を経る横断面のＡｕｇｅｒ電子顕微鏡解析によって測定した）。これらのサンプルを用いて溶液の性能を評価した。２１ないし２３℃にて２０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルバイアスの横断面をとり、次いで電界放射走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表２６に示す。
【表３２】

【０１２２】
表２６によれば、データはある範囲のＣｙＤＴＡ濃度が有用であるということを示している。
【０１２３】
実施例２８
水溶液「Ｐ８」は０．４０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１９．２重量％ヒドラジンを用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｐ９」は４．３３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．０８８重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１２重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１５．７重量％ホルムアルデヒドを用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｐ１０」は０．２６重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、１１．５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１３重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１６．７重量％メチルアミンを用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。その基盤においてアルミ銅金属を露出する誘電層および窒化チタン層を貫通する０．５ミクロンの深度の孔（バイアス）に対して０．３ないし０．５ミクロンの幅を有するウェーハーサンプル＃１１は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機チタン含有残渣を後に残すことで予め製造した（残渣を経る横断面のＡｕｇｅｒ電子顕微鏡解析によって測定した）。これらのサンプルを用いて溶液の性能を評価した。３５℃にて２０ないし３０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルバイアスの横断面をとり、次いで電界放射走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表２７に示す。
【表３３】

【０１２４】
表２７によれば、データは他の低分子はチタン残渣除去に効果がないということを示している。ヒドロキシルアミンと同様に、ヒドラジンは強力な還元剤である。ヒドラジンに有効性がないということは予想されず、珪酸塩含有処方を用いて、ウェーハーサンプル＃１１に見られるチタン含有残渣をバイアスから洗浄することができるのは、ヒドロキシルアミンと過酸化水素特有のものであるということを証明している。
【０１２５】
実施例２９
水溶液「Ｌ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面化性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および３重量％グリセロールを加えて調製した。なお、この溶液の残部は水であり、ｐＨは約１２．１である。水溶液「Ｍ１」は１．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）、１８．５重量％ヒドロキシルアミンおよび０．０７重量％非イオン界面化性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｐ８」は０．４０重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１０重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１９．２重量％ヒドラジンを用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｓ１」は５８３グラム脱イオン水、７．８グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および８．６グラム珪酸テトラメチルアンモニウム（ＴＭＡＳ、Ｓｉ０₂として１０．０％）を合することにより調製し、このｐＨは１２．５である。水溶液「Ｓ２」は９９．０グラム溶液「Ｓ１」と２．５グラムβ−シクロデキストリンを合することによって調製した（溶液ｐＨ＝１２．１）。水溶液「Ｓ３」は９９．０グラム溶液「Ｓ１」と２．５グラム次亜リン酸ナトリウムを合することによって調製した（溶液ｐＨ＝１２．３）。水溶液「Ｓ４」は９９．０グラム溶液「Ｓ１」と２．５グラム亜ジチオン酸ナトリウムを合することによって調製した（溶液ｐＨ＝６．７）。水溶液「Ｓ５」は９９．０グラム溶液「Ｓ１」と２．５グラム亜硫酸ナトリウムを合することによって調製した（溶液ｐＨ＝１２．３）。保存水溶液「Ｓ５ｂ」は１，７７５．２グラム脱イオン水および９６．０グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液、８．８グラムトランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）および１１４．８グラム珪酸テトラメチルアンモニウム（ＴＭＡＳ、Ｓｉ０₂として１０．０％）を合することによって調製した。保存水溶液「Ｓ５ｃ」は９００ｍｌ脱イオン水および３００ｍｌ溶液「Ｓ５ｂ」を合することによって調製した。水溶液「Ｓ６」は８０．０グラム溶液「Ｓ５ｃ」、５．０グラムＬ−アスコルビン酸および１８．２グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液を合することによって調製した（溶液ｐＨ＝１２．３）。水溶液「Ｓ７」は８０．０グラム溶液「Ｓ５ｃ」、５．０グラムヒドロキノンおよび２７．１グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液を合することによって調製した（溶液ｐＨ＝１２．４）。水溶液「Ｓ８」は８０．０グラム溶液「Ｓ５ｃ」、５．０グラムＬ（＋）−システインおよび２９．６グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液を合することによって調製した（溶液ｐＨ＝１２．４）。水溶液「Ｓ９」は８０．０グラム溶液「Ｓ５ｃ」、１０．０グラム過硫酸アンモニウムおよび３２．９グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液を合することによって調製した（溶液ｐＨ＝１２．６）。水溶液「Ｓ１０」は８０．０グラム溶液「Ｓ５ｃ」、５．０グラム硝酸および１０．２グラム水酸化テトラメチルアンモニウム五水和物（ＴＭＡＨ）を合することによって調製した（溶液ｐＨ＝１２．４）。水溶液「Ｓ１１」は９０．０グラム溶液「Ｓ５ｃ」、５．０グラムおよび１９．２グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液を合することによって調製した（溶液ｐＨ＝１２．３）。水溶液「Ｓ１２」は８０．０グラム溶液「Ｓ５ｃ」、５．０グラム８８％蟻酸、１０．０グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および１２．７グラム水酸化テトラメチルアンモニウム五水和物（ＴＭＡＨ）を合することによって調製した（溶液ｐＨ＝１２．６）。水溶液「Ｓ１３」は８０．０グラム溶液「Ｓ５ｃ」、５．０グラム硫酸および１７．５グラム水酸化テトラメチルアンモニウム五水和物（ＴＭＡＨ）を合することによって調製した（溶液ｐＨ＝１２．３）。水溶液「Ｓ１４」は８０．０グラム溶液「Ｓ５ｃ」、５．０グラムのリン酸および２０．１グラム水酸化テトラメチルアンモニウム五水和物（ＴＭＡＨ）を合することによって調製した（溶液ｐＨ＝１２．３）。水溶液「Ｓ１５」は８０．０グラム溶液「Ｓ５ｃ」、６．０グラム蓚酸二水和物、１６．０グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および９．３グラム水酸化テトラメチルアンモニウム五水和物（ＴＭＡＨ）を合することによって調製した（溶液ｐＨ＝１２．６）。水溶液「Ｓ１６」は８０．０グラム溶液「Ｓ５ｃ」、５．０グラムカテコールおよび１６．１グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液を合することによって調製した（溶液ｐＨ＝１２．４）。各溶液を１２５ｍｌポリエチレン瓶に入れ、固く蓋を締めて４５℃に設定したオーブンに入れて１時間予熱した。０．０２５ｍｍ×１３ｍｍ×５０ｍｍ、９９．９４％純度チタン箔片を脱イオン水、アセトンですすぎ、乾燥させ、次いで化学天秤で秤量した。１時間予熱した後、各溶液をオーブンから取り出し、次いでチタン箔片を瓶に入れ、再び固く蓋をしてオーブンに戻した。約４５℃にて２４時間後、瓶をオーブンから取り出した。チタン箔片を取り出し、脱イオン水ですすぎ、次いでアセトンですすぎ、乾燥させてさらに化学天秤で秤量した。重量損失から相対的腐食度を求めた。結果を表２８に示す。
【表３４】

【０１２６】
表２８によれば、データは４５℃という低い処理温度では、上記の試験した可能性あるチタン残渣除去促進剤のすべて（ヒドロキシアミンを除く）が効果がなかったということを示している。ここで示されるヒドラジンに有効性がないということが実施例２８で示されたＦＥ−ＳＥＭ結果を確かなものにしている。示された結果は、相対的チタンエッチング（除去）速度を速めるのは、ヒドロキシルアミン特有のものであるということを証明している。
【０１２７】
実施例３０
水溶液「Ｒ１」は５８３グラム脱イオン水、４．６８グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および８．６４グラムの珪酸テトラメチルアンモニウム（ＴＭＡＳ、Ｓｉ０₂として１０．０％）および０．６６グラムトランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）を合することにより調製し、このｐＨは１１．３である。水溶液「Ｒ２」は９９．０グラム溶液「Ｒ１」、０．３３グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および１．０グラムヒドロキシルアミン５０％水溶液を合することにより調製した（溶液ｐＨ＝１２．０）。水溶液「Ｒ３」は９９．０グラム溶液「Ｒ１」、０．３４グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および５．０グラムヒドロキシルアミン５０％水溶液を合することにより調製した（溶液ｐＨ＝１１．９）。水溶液「Ｒ４」は９９．０グラム溶液「Ｒ１」、０．３４グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および１０．０グラムヒドロキシルアミン５０％水溶液を合することにより調製した（溶液ｐＨ＝１１．６）。水溶液「Ｒ５」は９９．０グラム溶液「Ｒ１」、０．５２グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および１．０グラムヒドロキシルアミン５０％水溶液を合することにより調製した（溶液ｐＨ＝１２．２）。水溶液「Ｒ６」は９９．０グラム溶液「Ｒ１」、０．５４グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および５．０グラムヒドロキシルアミン５０％水溶液を合することにより調製した（溶液ｐＨ＝１２．０）。水溶液「Ｒ７」は９９．０グラム溶液「Ｒ１」、０．５６グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および１０．２グラムヒドロキシルアミン５０％水溶液を合することにより調製した（溶液ｐＨ＝１１．８）。保存水溶液「Ｒ８」は５８３グラム脱イオン水、４．６８グラム水酸化テトラメチルアンモニウム（ＴＭＡＨ）２５％水溶液および８．６４グラム珪酸テトラメチルアンモニウム（ＴＭＡＳ、Ｓｉ０₂として１０．０％）を合することにより調製し、このｐＨは１２．０である。水溶液「Ｒ９」は９４．０グラム溶液「Ｒ８」および２０．０グラムヒドロキシルアミン５０％水溶液を合することにより調製した（溶液ｐＨ＝１１．３）。各溶液を１２５ｍｌポリエチレン瓶に入れ、固く蓋を締めて４５℃に設定したオーブンに入れて１時間予熱した。０．０２５ｍｍ×１３ｍｍ×５０ｍｍ、９９．９４％純度チタン箔片を脱イオン水、アセトンですすぎ、乾燥させ、次いで化学天秤で秤量した。１時間予熱した後、各溶液をオーブンから取り出し、次いでチタン箔片を瓶に入れ、再び固く蓋をしてオーブンに戻した。約４５℃にて２４時間後、瓶をオーブンから取り出した。チタン箔片を取り出し、脱イオン水ですすぎ、次いでアセトンですすぎ、乾燥させてさらに化学天秤で秤量した。重量損失から相対的腐食度を求めた。結果を表２９に示す。
【表３５】

【０１２８】
表２９によれば、データはチタン残渣除去促進剤ヒドロキシルアミンの濃度が高まるにつれ、相対的チタン箔除去度も高まるということを示している。本試験におけるチタン除去度はウェーハーサンプル＃１１の洗浄における有効性に正比例している。
【０１２９】
実施例３１
水溶液「Ｍ１」は１．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）１８．５重量％ヒドロキシルアミンおよび０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｐ１」は２．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．６重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１１．５である。比較のために使用した市販のエッチング後残渣リムーバーはＥＫＣ−２６５^TM（EKC Technology, Inc.の製品）およびＡＣＴ−９３５ＴＭ（ACT Inc.の製品）であった。その基盤においてアルミ銅金属を露出する誘電層および窒化チタン層を貫通する０．５ミクロンの深度の孔（バイアス）に対して０．３ないし０．５ミクロンの幅を有するウェーハーサンプル＃１１は、（ａ）アルミ銅、次いで窒化チタンでメッキし、（ｂ）化学蒸着を用いて酸化珪素誘電体で被覆し、（ｃ）フォトレジスト材料を用いてバイアスのリトグラフパターンをとり、（ｄ）反応性イオンエッチングを用いてパターンを誘電層に転写し、（ｅ）酸素プラズマ灰化により残存するフォトレジストの大部分を除去し、一方主に無機チタン含有残渣を後に残すことで予め製造した（残渣を経る横断面のＡｕｇｅｒ電子顕微鏡解析によって測定した）。これらのサンプルを用いて溶液の性能を評価した。３５℃にて２０分間溶液にウェーハーサンプルを入れて取り出し、脱イオン水ですすぎ、加圧窒素ガスで乾燥させた。乾燥後、サンプルバイアスの横断面をとり、次いで電界放射走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察して起伏の洗浄および／または腐食の程度を求めた。結果を表３０に示す。
【表３６】

【０１３０】
表３０によれば、データは３５℃という低い工程温度で、本発明の組成物がチタンを含有することが知られている残渣を除去するのに有効であったということを示している。このデータはまた、低温洗浄のためのチタン残渣除去促進剤ヒドロキシルアミンの使用が本発明の組成物特有のものであるということを示している。
【０１３１】
実施例３２
水溶液「Ｌ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および３重量％グリセロールを加えて調製した。なお、この溶液の残部は水であり、このｐＨは約１２．１である。水溶液「Ｍ１」は１．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）１８．５重量％ヒドロキシルアミンおよび０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｐ１」は２．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．６重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１１．５である。水素シルセスキオキサン（ＨＳＱ）低ｋ誘電体の硬化層を有するシリコーンウェーハーサンプルをフーリエ変換赤外（ＦＴＩＲ）分光計に入れ、参照スペクトルをとった。ＨＳＱはその構造中にＳｉ−Ｈ結合を有しており、それは２１００ｃｍ^-1にあることが明らかである。次いで、室温にて（約２２℃）１０分間上記の溶液の１種中でウェーハーサンプルを処理し、脱イオン水ですすぎ、さらに乾燥させた。次いで、サンプルをＦＴＩＲに入れ、第２のスペクトルを得た。約２１００ｃｍ^-1のＳ−Ｈピーク面積を参照スペクトルに対して処理ウェーハースペクトルを比較するために用いた。比較のため、市販のエッチング後残渣リムーバー、ＥＫＣ−２６５^TM（EKC Technology, Inc.の製品）もまた同様にして、６５℃という製造業者の推奨温度で（１０分）試験した。結果を表３１に示す。
【表３７】

【０１３２】
表３１によれば、データは本発明の組成物はそれらがＨＳＱなどの感光性低ｋ誘電物質と適合するという点で独特であるということを示している。
【０１３３】
実施例３３
水溶液「Ａ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５（Air Products and Chemicals, Inc.の製品）および０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）を加えて調製し（この溶液の残部は水）、このｐＨは約１２．２である。水溶液「Ｌ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および３重量％グリセロールを加えて調製した。なお、この溶液の残部は水であり、このｐＨは約１２．１である。水溶液「Ｍ１」は１．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）１８．５重量％ヒドロキシルアミンおよび０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｐ１」は２．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．６重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１１．５である。保存水溶液「Ｔ１」は１．６重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．２７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．５６重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１２重量％グリセロールを加えて調製した。なお、この溶液の残部は水であり、このｐＨは約１２．５である。水溶液「Ｔ２」は２５ｍｌ溶液「Ｔ１」を７０ｍｌ脱イオン水および５ｍｌグリセロールで希釈することにより調製した。水溶液「Ｔ３」は２５ｍｌ溶液「Ｔ１」を６５ｍｌ脱イオン水および１０ｍｌグリセロールで希釈することにより調製した。水溶液「Ｔ４」は２５ｍｌ溶液「Ｔ１」を６０ｍｌ脱イオン水および１５ｍｌグリセロールで希釈することにより調製した。水溶液「Ｔ５」は２５ｍｌ溶液「Ｔ１」を５５ｍｌ脱イオン水および２０ｍｌグリセロールで希釈することにより調製した。水溶液「Ｔ６」は２５ｍｌ溶液「Ｔ１」を５０ｍｌ脱イオン水および２５ｍｌグリセロールで希釈することにより調製した。水溶液「Ｔ７」は２５ｍｌ溶液「Ｔ１」を２５ｍｌ脱イオン水および５０ｍｌグリセロールで希釈することにより調製した。水溶液「Ｔ８」は２５ｍｌ溶液「Ｔ１」を７５ｍｌグリセロールで希釈することにより調製した。水溶液「Ｔ９」は２５ｍｌ溶液「Ｔ１」を７０ｍｌ脱イオン水および５ｍｌ１−（２−ヒドロキシエチル）−２−ピロリジノン（ＨＥＰ）で希釈することにより調製した。水溶液「Ｔ１０」は２５ｍｌ溶液「Ｔ１」を６５ｍｌ脱イオン水および１０ｍｌ１−（２−ヒドロキシエチル）−２−ピロリジノン（ＨＥＰ）で希釈することにより調製した。水溶液「Ｔ１１」は２５ｍｌ溶液「Ｔ１」を６０ｍｌ脱イオン水および１５ｍｌ１−（２−ヒドロキシエチル）−２−ピロリジノン（ＨＥＰ）で希釈することにより調製した。水溶液「Ｔ１２」は２５ｍｌ溶液「Ｔ１」を５５ｍｌ脱イオン水および２０ｍｌ１−（２−ヒドロキシエチル）−２−ピロリジノン（ＨＥＰ）で希釈することにより調製した。水溶液「Ｔ１３」は２５ｍｌ溶液「Ｔ１」を５０ｍｌ脱イオン水および２５ｍｌ１−（２−ヒドロキシエチル）−２−ピロリジノン（ＨＥＰ）で希釈することにより調製した。水溶液「Ｔ１４」は２５ｍｌ溶液「Ｔ１」を２５ｍｌ脱イオン水および５０ｍｌの１−（２−ヒドロキシエチル）−２−ピロリジノン（ＨＥＰ）で希釈することにより調製した。水溶液「Ｔ１５」は２５ｍｌ溶液「Ｔ１」を７５ｍｌ１−（２−ヒドロキシエチル）−２−ピロリジノン（ＨＥＰ）で希釈することにより調製した。各溶液を１２５ｍｌポリエチレン瓶に入れ、固く蓋を締めて４５℃、６５℃または８５℃に設定したオーブンに入れて１時間予熱するか、または室温（約２２℃）で保持した。０．０２５ｍｍ×１３ｍｍ×５０ｍｍ、純粋な銅箔片を希塩酸に浸漬し、脱イオン水、アセトンですすぎ、乾燥させ、次いで化学天秤で秤量した。１時間予熱した後、各溶液をオーブンから取り出し（加熱した場合は）、次いで銅箔片を瓶に入れ、再び固く蓋をしてオーブンに戻した。約２２ないし８５℃で２４時間後、瓶をオーブンから取り出した。銅箔片を取り出し、脱イオン水ですすぎ、次いでアセトンですすぎ、乾燥させてさらに化学天秤で秤量した。重量損失から腐食度を求めた。比較のため、市販のエッチング後残渣リムーバー、ＥＫＣ−２６５^TM（EKC Technology, Inc.の製品）、ＥＫＣ−２７０^TM（EKC Technology, Inc.の製品）、ＥＫＣ−３１１^TM（EKC Technology, Inc.の製品）、ＡＣＴ−９３５ＴＭ（ACT Inc.の製品）、ＡＣＴ ＮＰ−９３７^TM（ACT Inc.の製品）およびＡＣＴ−９４１ＴＭ（ACT Inc.の製品）も、６５℃という製造業者の推奨温度で同様にして試験した。結果を表３２に示す。
【表３８】

【０１３４】
表３２によれば、データは本発明の数種の組成物が銅に適合するということを示している。データはまた、本発明の組成物Ｍ１は、銅メッキとともに使用するには、市販のヒドロキシルアミン含有エッチング後残渣リムーバー処方よりも優れているということを示している。さらに、データはチタン残渣除去促進剤過酸化水素を添加することで、銅腐食度が減少するということを示している。
【０１３５】
実施例３４
水溶液「Ｌ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および３重量％グリセロールを加えて調製した。なお、この溶液の残部は水であり、このｐＨは約１２．１である。クリーンルーム内で、ウェーハー粒子カウンターを用いて６５０オングストロームの熱酸化物を有する３インチのシリコーンウェーハー上に見られる総粒子を計測した（０．１ないし１０ミクロンの大きさ）。次いで、ウェーハーをアルミナベースの研磨スラリーで化学機械研磨し（ＣＭＰ）、さらに脱イオン水ですすいだ。次いで、溶液「Ｌ」を室温（約２２℃）で使用してウェーハーを「ブラシ洗浄」し、さらに脱イオン水ですすいで遠心脱水した。次いで、ウェーハー粒子カウンターを用いて洗浄後にウェーハー表面上に存在する総粒子（０．１ないし１０ミクロンのサイズ）を計測した。比較のため、ＣＭＰ後「ブラシ洗浄剤」に脱イオン水を使用した第２のウェーハーを試験した。結果を表３３に示す。
【表３９】

【０１３６】
表３３によれば、データは本発明の組成物はそれらが化学機械研磨後に生じる粒子混入物を除去することから独特のものであるということを示している。
【０１３７】
実施例３５
水溶液「Ｌ」は０．３重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および３重量％グリセロールを加えて調製した。なお、この溶液の残部は水であり、このｐＨは約１２．１である。水溶液「Ｍ１」は１．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．４５重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）、１８．５重量％ヒドロキシルアミンおよび０．０７重量％非イオン界面活性剤Ｓｕｒｆｙｎｏｌ−４６５を用いて調製し（この溶液の残部は水）、このｐＨは約１２．１である。水溶液「Ｐ１」は２．２重量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）、０．１１重量％トランス−（１，２−シクロヘキシレンジニトリロ）四酢酸（ＣｙＤＴＡ）、０．１４重量％（Ｓｉ０₂％換算）珪酸テトラメチルアンモニウム（ＴＭＡＳ）および１．６重量％過酸化水素を用いて調製し（この溶液の残部は水）、このｐＨは約１１．５である。約６５０ｎｍの熱酸化物を有する同一のＳｉ（１００）ウェーハーからの切片をアセトンですすぎ、乾燥させ、さらにＲｕｄｏｌｐｈ ＦＴＭ干渉計で測定して熱酸化物の厚みを求めた。４つの範囲を測定し処理後の追跡測定のためにマッピングした。次いで、各サンプルを瓶に入れ、再びゆるく蓋を締めて予め４５℃に設定したオーブンに入れるか、または室温（約２２℃）に放置した。約２２℃または約４５℃で２４時間後、瓶をオーブンから取り出してサンプルを取り出し、水洗し、次いでアセトンですすぎ、乾燥させて干渉計で測定した。サンプル上の４つの範囲に関して平均した熱酸化物フィルムの厚みの差異から相対的エッチング速度を求めた。比較のため、市販のエッチング後残渣リムーバー、ＥＫＣ−２６５^TM（EKC Technology, Inc.の製品）、ＥＫＣ−２７０^TM（EKC Technology, Inc.の製品）、ＥＫＣ−３１１^TM（EKC Technology, Inc.の製品）、ＡＣＴ−９３５^TM（ACT Inc.の製品）、ＡＣＴ ＮＰ−９３７^TM（ACT Inc.の製品）およびＡＣＴ−９４１^TM（ACT Inc.の製品）も、６５℃という製造業者の推奨温度で同様にして試験した。結果を表３４に示す。
【表４０】

*６５℃で１８時間試験
【０１３８】
表３４によれば、データは本発明の組成物がそれらがウェーハー基板から、誘電層の望ましくないエッチングを伴わずに望ましくない残渣を洗浄するという点で独特であるということを示している。これらの結果は珪酸塩含有組成物に関して実施例＃１５に示された結果と一致する。
【０１３９】
実施例は、本発明に関する１０の驚くべき、かつ、予想されなかった結果を示している。第１には、低い作業温度および短い作業時間で望ましくない金属腐食を防ぎつつウェーハー表面から望ましくない残渣を洗浄することができること。第２には、緩衝剤として珪酸塩を用い、希釈率が高く、高ｐＨの組成物（ｐＫａ＝１１．８）の予想されないほど高い液槽安定性。第３には、アルカリ度の高い洗浄剤へ添加された珪酸塩が集積回路に存在する酸化珪素誘電材の望ましくない溶解を阻害すること。第４には、組成物が極めて水性（典型的には＞８０％水）であるので、洗浄後腐食を防ぐための水洗の前に中間すすぎ工程が必要でないこと。第５には、これらの組成物の高い水分含量のために、典型的な有機フォトレジストストリッパーおよびプラズマ灰化後残渣リムーバーと比較して、使用および取扱いに伴う衛生上、安全上、および環境上のリスクが著しく小さいこと。第６には、本発明の組成物は、典型的な有機灰化後残渣リムーバーと比較して、処理後に基板表面上に炭素残渣の混入が実質的にほとんど残らないことが示されていること。第７には、本発明の組成物は集積回路に使用される感光性低ｋ誘電材料に適合するということが分かっていること。第８には、扱いにくいチタン含有残渣を低温で除去できること。第９には、本発明の組成物は銅金属に適合することが分かっていること。第１０には、本発明の組成物はまた、ウェーハー基板からシリカおよびアルミナ化学機械研磨（ＣＭＰ）スラリー残渣を除去する際にも有効であることが分かっていること。珪酸塩は公知のアルミニウム腐食阻害剤であるが、アルミニウム腐食を阻害し、さらに、典型的には高アルミニウムおよび／またはチタン含量の金属含有フォトレジスト残渣を選択的に除去できる能力は驚くべきものであり、かつ、予想されないものであった。処理の間の珪酸塩の緩衝作用、基板表面の無視できる炭素混入、低い誘電体エッチング度、感光性低ｋ誘電材料との適合性、銅金属との適合性、扱いにくいチタン含有残渣を低温で除去できる能力、シリカおよびアルミナ化学機械研磨（ＣＭＰ）スラリー残渣を洗浄する能力およびかかる高い水濃度を効果的に使用する能力もまた本発明の驚くべき、かつ、予想されない態様であった。
【０１４０】
上記の技術に鑑みて、本発明の多くの改良および変更が可能であることは明らかである。従って、本発明は、特に記載されたもの以外にも添付の請求の範囲内で実施され得るものと理解すべきである。[0001]
Background of the Invention
The present invention relates to a composition useful in the microelectronics industry for cleaning semiconductor wafer substrates. More particularly, the present invention relates to an alkaline stripping composition containing metal ion free silicate that is used to clean wafers having metal wiring and bias by removing metal or organic impurities without damaging the integrated circuit. Or relates to a cleaning composition.
[0002]
Description of prior art
Integrated parts of microelectronic molded products have photoresist applications that transfer images from a mask or reticle to a desired circuit layer. After the desired image transfer is made, the desired structure is formed using an etching method. The most common structure formed in this way is a metal wiring or a bias.
[0003]
This metal wiring is used to make electrical communication between various parts of the integrated circuit in the same mold layer. A bias is a hole that is etched down to the dielectric layer and later filled with a conductive metal. They are used to form electrical connections between different vertical layers of the integrated circuit. The methods used to form metal interconnects and bias generally use a halogen containing gas.
[0004]
After the etching process is complete, the photoresist mass can be removed by either chemical stripper solution or oxygen plasma ashing. The problem is that these etching steps produce very insoluble metal-containing residues that are not removed by conventional chemical stripper solutions. Also, during the ashing process, the metal-containing residue is oxidized and becomes more difficult to remove, particularly in the case of aluminum-based integrated circuits. See "Managing Etch and Implant Residue," Semiconductor Internatonal, August 1997, pages 56-63.
[0005]
An example of such an etching method is the embossing of metal wiring on an integrated circuit. In this method, after applying a photoresist coating to a metal film, drawing is performed through a mask or a reticle, and a pattern of the photoresist coating is selectively exposed. This coating is developed and either exposed or unexposed photoresist is removed depending on the color tone of the photoresist used to form a photoresist on the metal pattern. The remaining photoresist is usually recured at an elevated temperature to remove the solvent and optionally crosslink the polymer matrix. Next, an actual metal etching process is performed. This etching process removes the metal not covered with the photoresist through the action of gas plasma. By removing the metal, the pattern is transferred from the photoresist layer to the metal layer. The remaining photoresist is then removed (“strip”) with an organic stripper solution or oxygen plasma ashing. This ashing method is often followed by a washing step using an organic stripper solution. However, currently available stripper solutions, usually alkaline stripper solutions, leave insoluble metal oxides or other metal-containing residues in the integrated circuit.
[0006]
  Another example of such an etching method is embossing a bias (internal communication hole) on an integrated circuit. In this method, after applying a photoresist coating to a dielectric film, drawing is performed through a mask or a reticle, and a pattern of the photoresist coating is selectively exposed. This coating is developed and either exposed or unexposed photoresist is removed depending on the color tone of the photoresist used to form a photoresist on the metal pattern. The remaining photoresist is usually recured at an elevated temperature to remove the solvent and optionally crosslink the polymer matrix. Next, an actual metal etching process is performed. This etching removes the dielectric not covered with the photoresist through the action of gas plasma. By removing the dielectric, the pattern is transferred from the photoresist layer to the dielectric layer. The remaining photoresist is then removed (“strip”) with an organic stripper solution or oxygen plasma ashing. Typically, the dielectric is etched to the point where the underlying metal layer is exposed. Titanium or titanium nitride anti-reflective ordiffusionThe barrier layer is typically present at the metal / dielectric interface. This boundary layer is usually subjected to etching to expose the underlying metal. The action of etching the titanium or titanium nitride layer is the etching that forms titanium inside the biasResidueFound to be incorporated into. Oxygen plasma ashing oxidizes these bias residues and makes their removal more difficult. Therefore, a titanium residue removal etchant must be added to the stripper solution to allow cleaning of these residues. See "Removal of Titanium Oxide Grown on Titanium Nitride and reduction of Via Contact Resistance Using a Modern Plasma Asher", Mat. Res. Soc. Symp. Proc. Vol. 495, 1998, pages 345-352. Use organic stripper solution after ashingrinseThe process is often performed. However, currently available stripper solutions, usually alkaline stripper solutions, leave insoluble metal oxides and other metal-containing residues on the integrated circuit. There are several commercially available hydroxylamine-based strippers and post ash residue removers with high organic solvent content, but they are not effective for bias or other residues found in metal wiring. They also require high temperatures (typically above 65 ° C.) to clean residues from bias and metal wiring.
[0007]
  When using alkaline strippers on microcircuits containing metal films, especially aluminum, or aluminum or titaniumofWhen used with a combination of such active metals and higher positive metals such as copper or tungsten, ie, metal films containing alloys, a good quality circuit may not always be obtained. Various types of metal corrosion have been observed, such as corrosion whiskers, pitting, and metal wiring notching, due at least in part to the reaction of the metal with the alkaline stripper. Furthermore, Lee et al., Proc. Interface '89, pp. 137-149 shows that very little corrosive action occurs until the water washing step required to remove the organic stripper from the wafer. This corrosion is clearly the result of contact between the metal and the strong alkaline aqueous solution present in the rinse. Aluminum metal corrodes rapidly under such conditions (Ambat et al., Corrosion Science, Vol. 33 (5), p. 684. 1992).
[0008]
Prior methods used to avoid such corrosion problems have used an intermediate rinse step with a non-alkaline organic solvent such as isopropyl alcohol. However, such methods are expensive and are undesirable for safety, chemical hygiene and environmental reasons.
[0009]
The prior art discloses several organic strippers that are used to remove the photoresist mass after the etching process. U.S. Pat. Nos. 4,765,844, 5,102,777, and 5,308,745 disclose photoresist strippers containing various combinations of organic solvents. However, these strippers are not very effective for wafers "ashed" with oxygen plasma as described above. Some photoresist strippers attempt to address this problem by adding additional water and organic corrosion inhibitors such as catechol. Such compositions are described in U.S. Pat. Nos. 5,482,566, 5,279,771, 5,381,807, 5,334,332, 5,709,756, Nos. 5,707,947 and 5,419,779, and WO9800244. In some cases, hydroxylamine, which is also a hydrazine derivative, is added. Due to its toxicity, the use of catechol raises various environmental, safety and hygiene concerns.
[0010]
  The cleaning liquid used for the electric circuit board contains silicate metal as a corrosion inhibitor. Examples of such cleaning liquids are disclosed in SU761976, DD143,920, DD243,921, US5,264,046, US5,234,505, US5,234,506 and 5,393,448. The metal wiring on the circuit board is much larger than that found in integrated circuits, so cleaningRequirements for requirementsIs small. In the case of integrated circuits, metal contamination resulting from the cleaning solution can cause premature device failure even at very low concentrations. Therefore, any of the formulations deliberately added with metals such as the metal silicates listed above will impair the performance and reliability of the integrated circuit device. U.S. Pat. No. 4,659,650 discloses using a sodium metasilicate solution to dissolve a metal lifted mask.
[0011]
  US 5,817,610 and EP 829,768 disclose the use of quaternary ammonium silicate, quaternary ammonium hydroxide and water for use in removing plasma etching residues. In these two disclosures, catechol origimer is preferred over quaternary ammonium silicate as a corrosion inhibitor.TheNo examples of quaternary ammonium silicates used as corrosion inhibitors are shown. US 5,756,973 and EP 828,197 disclose the use of quaternary ammonium silicates, amine compounds, water and optionally organic polar solvents for use as stripping and cleaning compositions. None of the four disclosures listed above disclose the benefits of adding an aminocarboxylic acid buffer or a titanium residue removal accelerator. The four disclosures listed above do not disclose the advantages of adding a titanium residue removal accelerator. The present invention shows that in order to effectively clean the titanium-containing residues found after the plasma etching step in some cases, it is necessary to add a titanium residue removal accelerator. US 5,759,973 and EP 828,197 disclose the use of chelators selected from sugars such as glucose, fructose or sucrose and sugar alcohols such as xylitol, mannitol and sorbitol. Laboratory testing of the formulations of the present invention with addition of fructose or sorbitol resulted in solutions that were not as stable as formulations containing aminocarboxylic acids or that did not contain chelating or buffering agents.
[0012]
Patent application WO9523999 discloses the use of tetramethylammonium silicate and ammonium silicate as corrosion inhibitors in the solution used to remove the resist originating from the circuit board. However, it is said that the advantage of the disclosed formulation is that it does not contain (ethylenedinitrilo) tetraacetic acid (EDTA). In contrast, in the present invention, the use of an optional chelating agent such as EDTA was beneficial.
[0013]
Other uses of the silicate inhibitor include magnetic head cleaner (JP09, 245, 311), laundry detergent (WO9,100,330), metal treatment liquid (DE2,234,842, US3,639,185, US3). 773,670, US 4,351,883, US 4,341,878, EP 743,357, US 4,710,232), rosin flux remover (US 5,549,761) and photoresist (JP 50, 101, 103). It is done.
[0014]
  Both metal ion free silicates such as tetramethylammonium silicate and silicate metals are used as components of photoresist developers (US 4,628,023, JP 63,147,163, US 4,822,722, US 4,931). , 380, RD318,056, RD347,073, EP62,733). Photoresist developer removes modified photoresist embossed areas by exposure before etching and oxygen plasma ashing processUsed forIs done. This leaves a photoresist pattern on the wafer surface that is typically exposed and exposed.YoAndAddition“Curing” by heat to form an etching mask. This mask is used during plasma etching process and oxygen plasma “ashing” processInYokoThisUsually removed after use. The present invention relates to the removal of residues formed during these last two steps, and not to the photoresist development process handled by the patent set forth in this paragraph.
[0015]
A solution of tetramethylammonium hydroxide (TMAH) in silicic acid or solid silicone has been reported to be useful for passivation of aluminum during micromachining ("Aluminum passivation in Saturated TMAHW Solution for IC-Compatible Microstructures and Device Isolation ", Sarrow et al., SPIE Vol. 2879, Proceedings- Micromachining and Microfabrication Process Technology II, The International Society for Optical Engineering, Oct. 14-15, 1996, pp. 242-250). The application of micromachining is outside the scope of the present invention. The solutions in the cited references are about 25% by weight silicate (SiO 2₂Conversion). This concentration is the concentration used in the examples of the present invention, ie, about 0.01 to about 2.9% by weight silicate (SiO₂Remarkably higher). The use of the chelating agent catechol as a silicone etch rate enhancer is also proposed. In the present invention, the increased etch rate of silicone is undesirable because it can damage the silicon dioxide dielectric layer commonly used in integrated circuits, as well as the exposed silicone on the backside of the wafer.
[0016]
The use of quaternary ammonium hydroxide in photoresist strippers is disclosed in US Pat. No. 4,776,892, US Pat. No. 5,563,119, JP093199098 A2, EP578570 A2, WO91117484 A1 and US Pat. No. 4,776,892. The use of chelating agents and complexing agents for sequestering in various detergents is also described in WO 9705228, US 5,466,389, US 5,498,293, EP 812011, US 5,561,105, JP0621 773, JP06250400, JP06250400 and GB1. 573, 206.
[0017]
US Pat. No. 5,466,389 discloses an aqueous alkaline solution containing a cleaning solution for microelectronic substrates containing quaternary ammonium hydroxide and optionally a metal chelator and is effective for a pH range of about 8-10. . In the present invention, a pH higher than 10 is required to achieve the desired residue removal. Furthermore, the silicate has limited water solubility at about pH 10. In laboratory tests, when the pH of the tetramethylammonium silicate solution drops to about 10, the solution becomes “cloudy” as silicic acid precipitates from the solution.
[0018]
US 5,498,293 discloses a method using an aqueous alkaline cleaning solution containing a quaternary ammonium hydroxide and optionally a metal chelating agent useful for cleaning silicon wafers. This cleaning method disclosure is for processing on a substrate prior to the presence of an integrated metal circuit, which is used to substantially eliminate silicon dioxide and for integrated circuit sub-fabricated products. Used before using photoresist. In contrast, the present invention focuses on the cleaning of wafers with existing integrated circuits that are photoresist coated, etched, and oxygen plasma ashed.
[0019]
None of the compositions disclosed in the prior art can effectively remove all organic contaminants and metal-containing residues remaining after a typical corrosion process. Accordingly, there is a need for a stripping composition that cleans semiconductor wafer substrates by removing metal and organic contaminants from such substrates without damaging the integrated circuit. Such compositions should not particularly corrode metal undulations comprising integrated circuits and should avoid costly and detrimental consequences attributed to an intermediate rinse step.
[0020]
Summary of the Invention
Accordingly, it is an object of the present invention to provide a composition useful in the microelectronics industry for cleaning semiconductor wafer substrates.
[0021]
Another object of the present invention is to provide a composition that removes metals and organic contaminants (contaminants) from a semiconductor wafer substrate without compromising the integrated circuit.
[0022]
Another object of the present invention is to provide a composition that avoids the costly and deleterious consequences associated with an intermediate rinse step.
[0023]
It is a further object of the present invention to provide a method for cleaning a semiconductor wafer substrate that removes metal and organic contaminants from such substrates without damaging the integrated circuit, and avoids costly and detrimental consequences attributed to an intermediate rinse step. That is.
[0024]
  These and other objectives are achieved using a novel aqueous composition for stripping or cleaning semiconductor wafer substrates containing one or more metal ion free bases and water soluble metal ion free silicates. . The composition may contain undesirable contaminants and / orThe residueSubstrate surfaceWashKeep in contact with the semiconductor wafer substrate for a sufficient time and temperature to clean.
[0025]
Preferably, the composition comprises from about 0.01% to about 2% by weight of one or more metal ion free bases dissolved in water in an amount sufficient to bring the pH to about 11 or higher.₂Conversion) water-soluble metal-free silicate.
[0026]
Any suitable base may be used in the composition of the present invention. Preferably such bases are selected from hydroxides and organic amines, most preferably quaternary ammonium hydroxides and ammonium hydroxides.
[0027]
Any suitable silicate may be used in the composition of the present invention. Preferably, the silicate is selected from quaternary ammonium silicates, most preferably tetramethylammonium silicate.
[0028]
  The composition of the present invention may contain other components such as chelating agents, organic cosolvents, titanium residue removal accelerators and surfactants. Chelating agents are present in amounts up to about 2% by weightThePreferably, the organic co-solvent is present in an amount up to about 20% by weight, the titanium residue removal accelerator is preferably present in an amount up to about 30% by weight, and the surfactant is about 0.00%. It is preferably present in an amount up to 5% by weight.
[0029]
The composition can be used to clean a substrate containing an integrated circuit or can be used to clean a substrate that does not contain an integrated circuit. If an integrated circuit is present, the composition removes contaminants without damaging the integrated circuit.
[0030]
  The method of cleaning a semiconductor wafer substrate of the present invention can remove the composition of the present invention from unwanted contaminants and / orThe residueSubstrate surfaceWashIt must be in contact with the semiconductor wafer substrate for a sufficient time and temperature to clean. The method includes both liquid bath and spray applications. Typically, the substrate is exposed to the composition for a suitable time and at a suitable temperature, rinsed with high purity deionized water and dried.
[0031]
The composition cleans the wafer substrate by removing metal and organic residues. Importantly, this cleaning method does not damage the integrated circuits on the wafer substrate and avoids the costly and detrimental consequences associated with the intermediate rinse steps required by previous methods.
[0032]
Other objects, advantages and novel features of the invention will become apparent from the following detailed description of the invention.
[0033]
Detailed Description of the Invention
The present invention provides a novel aqueous composition for stripping or cleaning a semiconductor wafer substrate comprising one or more metal ion free bases and a water soluble metal ion free silicate. Preferably, the present invention comprises a sufficient amount of one or more alkali metal ion free base components to make a solution of pH about 11 or higher, preferably about pH 11 to about pH 13, and about 0.01% To about 5%, preferably about 0.01% to about 2% by weight (SiO 2₂An aqueous alkaline stripping or cleaning composition comprising a metal ion-free water-soluble silicate.
[0034]
The composition may also contain a chelating agent in a weight concentration of about 0.01 to about 10%, usually about 0.01% to about 2%. Further optional ingredients include about 0.1% to about 80%, usually about 1% to about 30% by weight aqueous organic solvent, about 1% to about 50%, usually about 1% to about 30%. % By weight of titanium residue removal accelerator, and from about 0.01% to about 1%, preferably from about 0.01% to about 0.5% by weight of a water-soluble surfactant.
[0035]
The composition is an aqueous solution containing a base, silicate, optional ingredients, and water, if present, preferably high purity deionized water.
[0036]
  Any suitable base is included in the composition of the invention.useMay be. Such bases are preferably quaternary ammonium hydroxides, such as tetraalkylammonium hydroxides (usually containing hydroxy and alkoxy containing alkyl groups of 1 to 4 carbon atoms in the alkyl or alkoxy group). Most preferred among these alkaline substances are tetramethylammonium hydroxide and trimethyl-2-hydroxyethylammonium hydroxide (choline). Examples of other quaternary ammonium hydroxides that can be used include trimethyl-3-hydroxypropylammonium hydroxide, trimethyl-3-hydroxybutylammonium hydroxide, trimethyl-4-hydroxybutylammonium hydroxide, triethyl hydroxide- 2-hydroxyethylammonium hydroxide, tripropyl-2-hydroxyethylammonium hydroxide, tributyl-2-hydroxyethylammonium hydroxide, dimethylethyl-2-hydroxyethylammonium hydroxide, dimethyldi (2-hydroxyethyl) ammonium hydroxide, water Monomethyltri (2-hydroxyethyl) ammonium oxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyl-triethyl hydroxide Ammonium monomethyl tripropyl ammonium hydroxide, monomethyl tributylammonium hydroxide, monoethyl trimethyl ammonium hydroxide, monoethyl tributylammonium hydroxide, dimethyl diethylammonium hydroxide, hydroxide dimethyldibutyl ammonium, and mixtures thereof.
[0037]
Other bases that will function in the present invention include ammonium hydroxide, organic amines, especially 2-aminoethanol, 1-amino-2-propanol, 1-amino-3-propanol, 2- (2-aminoethoxy). ) Alkanolamines such as ethanol, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) ethylamine, and guanidine, 1,3-pentanediamine, 4-aminomethyl-1,8 Others such as octanediamine, aminoethylpiperazine, 4- (3-aminopropyl) morpholine, 1,2-diaminocyclohexane, tri (2-aminoethyl) amine, 2-methyl-1,5-pentanediamine and hydroxylamine These are strong organic bases. Alkaline solutions containing metal ions such as sodium or potassium can also function, but are not preferred because residual metal contamination can occur. Also useful are mixtures of these further alkaline components, in particular ammonium hydroxide and the above mentioned tetraalkylammonium hydroxides.
[0038]
Any suitable metal ion free silicate may be used in the composition of the present invention. Such silicates are preferably quaternary ammonium silicates such as tetraalkylammonium silicates (usually containing hydroxy and alkoxy containing alkyl groups of 1 to 4 carbon atoms in the alkyl or alkoxy groups). The most preferred metal ion free silicate component is tetramethylammonium silicate. Other suitable metal ion free silicate sources for the present invention may be generated in situ by dissolving one or more of the following materials in a highly alkaline detergent. Suitable metal ion free materials useful for producing silicates in detergents include solid silicone wafers, silicic acid, colloidal silica, fumed silica, or any other form of silicone or silica. Silicate metal such as sodium metasilicate may be used, but cannot be encouraged because of the adverse effect of metal contamination on the integrated circuit.
[0039]
The compositions of the present invention may also be formulated with a suitable metal chelating agent to increase the ability to retain the metal in the formulation solution and to enhance dissolution of metal residues on the wafer substrate. Typical examples of chelating agents useful for this purpose include the following organic acids and their isomers and salts: (ethylenedinitrilo) tetraacetic acid (EDTA), butylenediaminetetraacetic acid, cyclohexene-1,2 -Diaminetetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), N, N, N ', N'-ethylenediaminetetra (methylenephosphonic) acid (EDTMP) ), Triethylenetetramine hexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N, N, N ′, N′-tetraacetic acid (DHPTA), methyliminodiacetic acid, propylenediaminetetraacetic acid, nitrotriacetic acid (NTA), citric acid, tartaric acid, gluconic acid, sugar acid Glyceryl acid, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, lactic acid, salicylic acid, catechol, gallic acid, propyl gallate, pyrogallol, 8-hydroxyquinoline, and cysteine.
[0040]
A preferred chelating agent is an aminocarboxylic acid such as EDTA. This type of chelator has a high affinity for aluminum-containing residues typically found on metal wiring or bias after plasma “ashing”. Furthermore, the pKa value of this type of chelator includes a pKa value of about 12, which improves the performance of the composition of the present invention.
[0041]
The composition of the present invention may also contain one or more suitable water-soluble organic solvents. Suitable various organic solvents include alcohols, polyhydric alcohols, glycols, glycol ethers, N-methylpyrrolidinone (NMP), 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP) and the like. There are alkyl-pyrrolidinones such as 1-hydroxyalkyl-2-pyrrolidinone, dimethylformamide (DMA), dimethylacetamide (DMAc), sulfolane or dimethyl sulfoxide (DMSO). If further aluminum and / or aluminum copper alloy and / or copper corrosion protection is desired, these solvents can be added to reduce the corrosion rate of aluminum and / or aluminum copper alloy and / or copper. Also good. Preferred water-soluble organic solvents include polyhydric alcohols such as glycerol and 1-hydroxyalkyl-2-pyrrolidinones such as 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP).
[0042]
The compositions of the present invention may also include one or more suitable titanium residue removal accelerators. Various suitable titanium residue removal accelerators include hydroxylamine, hydroxylamine salts, peroxides, ozone and fluoride. Preferred titanium residue removal accelerators are hydroxylamine and hydrogen peroxide.
[0043]
  The compositions of the present invention may also include any suitable water soluble amphoteric, nonionic, cationic or anionic surfactant. The addition of a surfactant reduces the surface tension of the formulation and improves the wettability of the surface being cleaned.WashingThe action is improved. If further aluminum corrosion protection is desired, surfactants can be added to reduce the aluminum corrosion rate.
[0044]
Amphoteric surfactants useful in the compositions of the present invention include betaines and sulfobetaines such as alkylbetaines, amidoalkylbetaines, alkylsulfobetaines and amidoalkylsulfobetaines; amphoglynates, amphpropionates, Afocarboxylic acid derivatives such as fodiglycinate and amphodipropionate; iminodiacids such as alkoxyalkyliminodiacids or alkoxyalkyliminodiacids; amine oxides such as alkylamine oxides and alkylamidoalkylamine oxides; fluoro And alkyl sulfonates and fluorinated alkyl amphoteric substances; and mixtures thereof.
[0045]
Preferably, the amphoteric surfactant is cocoamidopropyl betaine, cocoamidopropyl dimethylbetaine, cocoamidopropylhydroxysultain, capryloamphodipropionate, cocoamidodipropionate, cocoamphopropionate, cocoamphohydroxyethyl Propionate, isodecyloxypropyliminodipropionic acid, lauryliminodipropionate, cocoamidopropylamine oxide and cocoamine oxide, and fluorinated alkyl amphoteric substances.
[0046]
Nonionic surfactants useful in the compositions of the present invention include acetyl diols, ethoxylated acetyl diols, fluorinated alkyl alkoxylates, fluorinated alkyl esters, fluorinated polyoxyethylene alkanols, many Examples thereof include fatty acid esters of polyhydric alcohols, polyoxyethylene monoalkyl ethers, polyoxyethylene diols, siloxane surfactants, and alkylene glycol monoalkyl ethers. Preferably, the nonionic surfactant is an acetylenic diol or an ethoxylated acetylenic diol.
[0047]
Anionic surfactants useful in the compositions of the present invention include carboxylates, N-acyl sarcosinates, sulfonates, sulfates, and mono- and diesters of orthophosphoric acid such as decyl phosphate. . Such an anionic surfactant is preferably a metal-free surfactant.
[0048]
Cationic surfactants useful in the compositions of the present invention include amine ethoxylates, dialkyldimethylammonium salts, dialkylmorpholinum salts, alkylbenzyldimethylammonium salts, alkyltrimethylammonium salts, and alkylpyridinium salts. Such a cationic surfactant is preferably a halogen-free surfactant.
[0049]
In a preferred embodiment of the invention, the composition comprises about 0.1 to 2% by weight tetramethylammonium hydroxide (TMAH) and about 0.01 to 1% by weight (SiO 2).₂This is an aqueous solution containing tetramethylammonium silicate (TMAS).
[0050]
In another embodiment of the invention, the composition comprises about 0.1 to 2% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), and about 0.01 to 1% by weight (SiO₂This is an aqueous solution containing tetramethylammonium silicate (TMAS).
[0051]
In another embodiment of the invention, the composition comprises about 0.1 to 2% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO₂Converted) tetramethylammonium silicate (TMAS), and an aqueous solution containing about 0.5 to 20% by weight of a polyhydroxy compound, preferably glycerol.
[0052]
In another embodiment of the invention, the composition comprises about 0.1 to 2% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO₂Converted) tetramethylammonium silicate (TMAS), about 0.5 to 20% by weight of a polyhydroxy compound, and about 0.01 to 0.3% by weight of a nonionic ethoxylated acetyl diol surfactant. It is.
[0053]
In another embodiment of the invention, the composition comprises about 0.1 to 2% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO₂Converted) tetramethylammonium silicate (TMAS) and about 0.5 to 20% by weight of alkyl-pyrrolidinone such as 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP), preferably 1- (2-hydroxy An aqueous solution containing ethyl) -2-pyrrolidinone (HEP).
[0054]
  In another embodiment of the invention, the composition comprises about 0.1 to 2% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO₂) Tetramethylammonium silicate (TMAS), and about 0.5 to 20% by weight of an alkyl-pyrrolidinone such as 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP), and about 0.01 to 0. 3% by weight of nonionic ethoxylated acetyl diolWorldIt is an aqueous solution containing a surfactant.
[0055]
  Of the present inventionpreferableIn an embodiment, the composition comprises about 0.1 to 10% by weight tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight (SiO 2₂Conversion) tetramethylammonium silicate (TMAS), and an aqueous solution containing about 1 to 10% by weight of hydrogen peroxide.
[0056]
  Another one of the present inventionpreferableIn an embodiment, the composition comprises about 0.1 to 9 wt% tetramethylammonium hydroxide (TMAH), about 0.01 to 4 wt% (SiO₂Conversion) tetramethylammonium silicate (TMAS), and an aqueous solution containing about 1 to 20% by weight of hydroxylamine.
[0057]
In another embodiment of the invention, the composition comprises about 0.1 to 10% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO₂Conversion) tetramethylammonium silicate (TMAS), and an aqueous solution containing about 1 to 10% by weight of hydrogen peroxide.
[0058]
In another embodiment of the invention, the composition comprises about 0.1 to 9% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 4% by weight (SiO 2)₂Conversion) tetramethylammonium silicate (TMAS), and an aqueous solution containing about 1 to 20% by weight of hydroxylamine.
[0059]
In another embodiment of the invention, the composition comprises about 0.1 to 10% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO₂Conversion) tetramethylammonium silicate (TMAS), about 1 to 10% by weight of hydrogen peroxide, and about 0.01 to 0.3% by weight of a nonionic ethoxylated acetyl diol surfactant. .
[0060]
In another embodiment of the invention, the composition comprises about 0.1 to 9% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 4% by weight (SiO 2)₂Conversion) tetramethylammonium silicate (TMAS), about 1 to 20% by weight hydroxylamine, and about 0.01 to 0.3% by weight nonionic ethoxylated acetyl diol surfactant.
[0061]
In all embodiments, the balance of the composition is water, preferably high purity deionized water.
[0062]
  As shown in the following examples, a composition containing only an alkaline base cannot obtain an effective cleaning effect without corroding the undulations of the aluminum metal integrated circuit. This example also includes (1) silicate buffering (pKa) to prevent aluminum metal integrated circuits from corrosion.₂= 11.8) shows the usefulness of adding soluble silicates to highly basic formulations to extend the bath life of these cleaning compositions and (3) to reduce the silicon dioxide dielectric etch rate. Further advantages of the composition of the present invention are as follows. (1) High water content (without intermediate rinsing (such as isopropanol))Immediate(2) Integrated circuit board is supported by preventing the corrosion of the metal after washing by assisting water washing, and only negligible carbon contamination occurs on the substrate surface)TheNon-toxic especially avoiding catechols, volatile organic solvents and organic amines characteristic of prior art compositions used for tripping and washingcomponentWith the use ofYes,Hygiene, safety, environmental and handling risks are low, (3) Titanium-containing residues are removed from integrated circuit boards at low temperaturesAbility to(4) compatibility of these compounding agents with photosensitive low-k dielectric materials used in integrated circuits, (5) compatibility with copper (low etching rate) and (6) the composition of the present invention, Wafer in post chemical mechanical polishing (CMP) operationsubstrateAbility to clean and prevent contamination.
[0063]
  The method of the present invention applies a contaminated substrate to a substrate surface.FromA semiconductor wafer substrate is cleaned by exposure to the composition of the present invention for a time and at a temperature sufficient to clean undesired contaminants. If desired, the substraterinse andThe composition and contaminants are removed and dried to remove excess solvent or rinse agent. The substrate can then be used for the intended purpose.
[0064]
Preferably, the method uses a liquid bath or spray application to expose the substrate to the composition. The liquid bath or spray washing time is generally from 1 minute to 30 minutes, preferably from 5 minutes to 20 minutes. The liquid bath or spray washing temperature is generally 10 ° C to 85 ° C, preferably 20 ° C to 45 ° C.
[0065]
  If necessary,rinseThe time is generally 10 seconds to 5 minutes at room temperature, preferably 30 seconds to 2 minutes at room temperature.Preferably deionized water is used to rinse the substrate.
[0066]
If necessary, drying of the substrate can be achieved by any combination of air evaporation, heating, centrifugation, or pressurized gas. A preferable drying method is to centrifuge for a time until the wafer substrate is dried under a flow of an inert gas such as nitrogen through a filter.
[0067]
  The method of the present invention comprises a semiconductor wafer substrate that has been previously oxygen plasma ashed to remove photoresist lumps, particularly silicone, silicon oxide, silicon nitride, tungsten, tungsten alloy, titanium, titanium alloy, tantalum, tantalum alloy, It is extremely effective for cleaning wafer substrates containing copper, copper alloys, aluminum, or aluminum alloy films. The method is undesirable for metal and organic contaminantsExcludingHowever, it does not cause unacceptable corrosion to the silicone, silicon oxide, silicon nitride, tungsten, tungsten alloy, titanium, titanium alloy, tantalum, tantalum alloy, copper, copper alloy, aluminum, or aluminum alloy film.
[0068]
Example
The following examples illustrate specific embodiments of the invention described herein. It will be apparent to those skilled in the art that various modifications and improvements are possible and are considered to be within the scope of the described invention.
[0069]
Experimental procedure
  The percentages shown in the examples are percentages by weight unless otherwise specified. Aluminum metal corrosion is expressed in terms of both metal loss% and general corrosion index. The general corrosion index given isVery fewSlight, mild, moderate, andStrict. A small amount of ammonium corrosion is considered acceptable,Very few, Or just a little. Mild, moderate orStrictCorrosion was considered unacceptable. The cleaning and corrosion data registrations obtained using a scanning electron microscope (SEM) or field emission scanning electron microscope (FE-SEM) are all of the difference between untreated and treated samples from the same wafer.EyeAccording to sight.
[0070]
Example 1
Aqueous solution “A” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 (product of Air Products and Chemicals, Inc.) and 0.14% by weight (SiO₂% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 12.2. Aqueous solution “B” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Prepared with the activator Surfynol-465 (the remainder of the solution is water), the pH is about 12.7. Aqueous solution “C” is 0.08 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 and 0.13% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 10.5. Aqueous solution “D” is 0.09 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Prepared with the activator Surfynol-465 (the remainder of the solution is water), the pH is about 9.6. The aqueous solution “E” is 0.1 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic Surfactant Surfynol-465 and 0.010 wt% (Si0₂% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 11.3. Aqueous solution “F” is 0.08 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic Prepared using the surfactant Surfynol-465 (the remainder of the solution is water), the pH is about 10.9. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using wafer # 1 sample with pre-manufactured 1 micron wide undulations and wiring formed with aluminum copper and capped with titanium nitride, while removing the organic photoresist residue by The performance of the solution was evaluated. Wafer samples were removed from each of these solutions at 21-65 ° C. for 5-10 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 1.
[Table 1]

[0071]
According to Table 1, the data show the ability of TMAS to prevent corrosion of aluminum relief associated with exposure to alkaline solutions, and by adding tetramethylammonium silicate to a tetramethylammonium hydroxide based cleaning solution, It shows that undesired integrated circuit corrosion is completely inhibited.
[0072]
Example 2
  The aqueous solution “G” is 2.0 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface. Activator Surfynol-465 and 0.13% by weight (Si0₂% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.6. Aqueous solution “H” is 0.09 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 and 0.14% by weight (Si0₂% Conversion) prepared by adding tetramethylammonium silicate (TMAS) (the remainder of the solution is water), and the pH is about 10.8. The aqueous solution “M” is 1.8 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface. Activator Surfynol-465 and1.3% By weight (Si0₂% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.0. Aqueous solution “N” is 1.9 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface Activator Surfynol-465 and 0.86 wt% (Si0₂% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.2. Aqueous solution “O” is 1.9 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic Surfactant Surfynol-465 and 0.70 wt% (Si0₂% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.2. The aqueous solution “P” is 1.9 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic Surfactant Surfynol-465 and 0.54 wt% (Si0₂% Conversion) prepared by adding tetramethylammonium silicate (TMAS) (the remainder of the solution is water), and the pH is about 13.3. Aqueous solution “Q” is 2.0 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic Surfactant Surfynol-465 and 0.45 wt% (Si0₂% Conversion) prepared by adding tetramethylammonium silicate (TMAS) (the remainder of the solution is water), and the pH is about 13.3. The aqueous solution “R” is 2.0% by weight tetramethylammonium hydroxide (TMAH), 0.1% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06% by weight nonionic. Surfactant Surfynol-465 and 0.28 wt% (Si0₂% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.4. The aqueous solution “S” is 2.0% by weight tetramethylammonium hydroxide (TMAH), 0.1% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07% by weight nonionic. Surfactant Surfynol-465 and 0.19 wt% (Si0₂% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.4. The aqueous solution “T” is 0.1 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic Surfactant Surfynol-465 and 0.020 wt% (Si0₂% Conversion) prepared by adding tetramethylammonium silicate (TMAS) (the remainder of the solution is water), and the pH is about 11.2. The aqueous solution “U” is 0.1 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic Surfactant Surfynol-465 and 0.070 wt% (Si0₂% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 10.9. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using wafer # 1 sample with pre-manufactured 1 micron wide undulations and wiring formed with aluminum copper and capped with titanium nitride, while removing the organic photoresist residue by The performance of the solution was evaluated. The wafer sample was removed from the solution at 21-65 ° C. for 5-20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 2.
[Table 2]

[0073]
  According to Table 2, the data show that to prevent or attenuate the corrosion of aluminum relief associated with exposure to these alkaline solutions,As it growsThere is a need to increase the concentration of TMASis thereIndicating that the optimum pH range of the solution of the present application is about 11-13.
[0074]
Example 3
Aqueous solution “I” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface Activator Surfynol-465, 0.13% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 5 wt% glycerol were added. The balance of this solution is water. Aqueous solution “J” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface Activator Surfynol-465, 0.13% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 6 wt% glycerol were added. The balance of this solution is water. Aqueous solution “K” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface Activator Surfynol-465, 0.12% by weight (Si0₂% Conversion) It was prepared by adding tetramethylammonium silicate (TMAS) and 10% by weight diethylene glycol (DEG). The balance of this solution is water. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using wafer # 1 sample with pre-manufactured 1 micron wide undulations and wiring formed with aluminum copper and capped with titanium nitride, while removing the organic photoresist residue by The performance of the solution was evaluated. The wafer sample was removed from the solution at 21-35 ° C. for 5-20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 3.
[Table 3]

[0075]
According to Table 3, the data show that the addition of a water-soluble organic solvent is advantageous for the ability to prevent or attenuate the corrosion of aluminum undulations associated with exposure to TMA-containing alkaline solutions. It shows that by adding a water-soluble solvent to an object, the cleaning time can be extended without corroding metal wiring existing in the integrated circuit.
[0076]
Example 4
  Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water. Wafer sample # 2 having a width of 1/2 micron for a 1 micron deep hole (bias) through the dielectric material exposing the aluminum copper metal on its substrate is (a) aluminum copper and then titanium nitride. Plating, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, and (d) applying the pattern to the dielectric layer using reactive ion etching (E) Pre-manufactured by removing most of the remaining photoresist by oxygen plasma ashing, while mainly leaving behind inorganic residues. Wafer sample # 3, having a width of 1 micron against a 1 micron deep tapered hole (bias) through the dielectric material exposing the aluminum copper metal on its substrate, is plated with (a) aluminum copper and then titanium nitride. (B) coated with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using photoresist material, and (d) transferring the pattern to the dielectric layer using reactive ion etching And (e) pre-manufactured by removing most of the remaining photoresist by oxygen plasma ashing, while mainly leaving behind inorganic residues. These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 20-21 ° C. for 10 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample was taken and then observed with a scanning electron microscope (SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 4.
[Table 4]

[0077]
According to Table 4, the data show that the addition of a water-soluble organic solvent is advantageous for the ability to prevent or attenuate the corrosion of aluminum undulations associated with exposure to TMA-containing alkaline solutions. It shows that by adding a water-soluble solvent to the object, it is possible to clean the bias without corroding the metal at the base of the bias.
[0078]
Example 5
  (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Wafer # 1 and # 4 samples with 1 micron wide relief and wiring formed with aluminum copper and capped with titanium nitride, pre-manufactured by removing the organic photoresist residues by Each was used to evaluate the performance of the solution. Wafer samples were removed from the solution at 11-65 ° C. for 5-30 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Tables 5A, 5B and 5C.
[Table 5]

[Table 6]

[Table 7]

[0079]
According to Tables 5A, 5B and 5C, the data show that both formulations have significant processing latitude with or without the addition of a water-soluble organic solvent (Solution “L”) (Solution “A”). Is shown. A comparison of Tables 5B and 5C also shows that the addition of water-soluble organic solvents (solution “L”) reduces the aluminum metal corrosion that occurs with extended process time and high temperatures, further improving processing latitude. Is shown. In Table 5B, where an organic solvent was added to the formulation, the observed corrosion range was only 0-4%, even with a cleaning temperature of 65 ° C. In Table 5C, where no organic solvent was added, 4% or more corrosion was observed with a cleaning time of 10 minutes or more. The data also shows the considerable processing latitude that can be obtained with the compositions of the present invention and that processing tolerance can be further improved by the addition of an optional water-soluble solvent.
[0080]
Example 6
  The aqueous solution “V” was 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.07 wt% nonionic surfactant Surfynol-465 and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water. Aqueous solution “W” is 0.6 wt% tetramethylammonium hydroxide (TMAH), 0.3 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 and 0.14% by weight (Si0₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water. Aqueous solution “X” is 0.7 wt% tetramethylammonium hydroxide (TMAH), 0.5 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 and 0.14% by weight (Si0₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using a wafer # 4 sample with pre-manufactured 1 micron wide undulations and wiring made of aluminum copper and capped with titanium nitride, while removing organic photoresist residues by The performance of the solution was evaluated. The wafer sample was removed from the solution at 20-21 ° C. for 5 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 6.
[Table 8]

[0081]
According to Table 6, the data show that good stripping performance is obtained over a wide range of CyDTA concentrations. In this way, the amount of chelating agent present can be adjusted to accommodate the sample being washed. More difficult samples may require this desired component to achieve complete washing. The data also indicates that chelating agents are optionally used in the compositions disclosed herein.
[0082]
Example 7
  The aqueous solution “Y” was 0.4 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using a wafer # 4 sample with pre-manufactured 1 micron wide undulations and wiring made of aluminum copper and capped with titanium nitride, while removing organic photoresist residues by The performance of the solution was evaluated. The wafer sample was removed from the solution at 20-21 ° C. for 5 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 7.
[Table 9]

[0083]
According to Table 7, the data indicate that good stripping performance can be obtained for formulations mixed with surfactants to improve substrate wetting, and optionally in the compositions disclosed herein. It shows that a surfactant is used.
[0084]
Example 8
An open tank aging experiment was performed using a standard tank for two different formulations. The first tank was operated at room temperature for 24.75 hours, and the second tank was operated at 45 ° C. for 24.75 hours. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using a wafer # 4 sample with pre-manufactured 1 micron wide undulations and wiring made of aluminum copper and capped with titanium nitride, while removing organic photoresist residues by The performance of the solution was evaluated. Wafer samples were placed in this bath for 10 minutes at 20 ° C. or 45 ° C., rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 8.
[Table 10]

[0085]
According to Table 8, the data show the benefits of silicate buffering during long-term open bath aging at room and elevated temperatures. No change in stripping performance occurred during this aging period. The data also shows that the compositions of the present invention are not subject to aging.
[0086]
Example 9
The aqueous solution “A1” was 0.27 wt% tetramethylammonium hydroxide (TMAH) and 0.14 wt% (SiO 2₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “A2” was 0.38 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% chelating agent (ethylenedinitrilo) tetraacetic acid (EDTA) and 0.14 wt% (SiO 2₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “A3” was 0.39 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% chelating agent diethylenetriaminepentaacetic acid (DETPA) and 0.14 wt% (SiO 2₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “A4” was 0.40 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% chelating agent triethylenetetramine hexaacetic acid (TTHA) and 0.14 wt% (SiO 2₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “A5” is 0.40 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% chelating agent 1,3-diamino-2-hydroxypropane-N, N, N ′, N′-tetraacetic acid It was prepared by adding (DHPTA) and 0.14 wt% (Si02% conversion) tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “A6” contains 0.47 wt% tetramethylammonium hydroxide (TMAH), 0.13 wt% chelator N, N, N ′, N′-ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and 0. 14% by weight (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). Each solution was placed in a 125 ml glass bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A piece of 0.05 mm × 12 mm × 50 mm, 99.8% purity aluminum foil was washed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 9.
[Table 11]

[0087]
  According to Table 9, the data show that adding a chelating agent is useful to increase the aluminum etch rate. To allow removal of metal residues found on the wafer after oxygen plasma ashing in an acceptable stripping temperature and time range, it may be necessary to increase the aluminum etch rate. The data can also be used as desired to obtain the desired aluminum etch rate for the inventive compositions herein.variousConstructionNo kiIt shows that a rate agent is used.
[0088]
Example 10
The aqueous solution “B1” was 0.22% by weight tetramethylammonium hydroxide (TMAH), 0.1% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.14% by weight (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “B2” was 0.30 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “B3” was 0.45% by weight tetramethylammonium hydroxide (TMAH), 0.30% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.14% by weight (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.2). The aqueous solution “B4” was 0.59% by weight tetramethylammonium hydroxide (TMAH), 0.50% by weight trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA) and 0.14% by weight (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.1). The aqueous solution “B5” was composed of 1.1 wt% tetramethylammonium hydroxide (TMAH), 1.0 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “B6” was 4.1% by weight tetramethylammonium hydroxide (TMAH), 4.8% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.13% by weight (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). Each solution was placed in a 125 ml polyethylene bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A 0.05 mm x 12 mm x 50 mm, 99.8% pure aluminum foil piece was rinsed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 10.
[Table 12]

[0089]
According to Table 10, the data show that the addition of a chelating agent is useful to increase the aluminum etch rate. To allow removal of metal residues found on the wafer after oxygen plasma ashing in an acceptable stripping temperature and time range, it may be necessary to increase the aluminum etch rate. The aluminum etch rate is directly proportional to the amount of chelating agent used. The data also indicate that chelating agents, optionally added at various concentrations, are used to obtain the desired aluminum etch rate for the inventive compositions herein.
[0090]
Example 11
The aqueous solution “C1” was 0.25 wt% tetramethylammonium hydroxide (TMAH) and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “C2” was 0.36 wt% choline and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “C3” was 0.76 wt% tetrabutylammonium hydroxide (TBAH) and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “C4” was 1.6 wt% methyltriethanolammonium hydroxide (MAH) and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “C5” was 0.36 wt% methyltriethylammonium hydroxide (MTEAH) and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). Each solution was placed in a 125 ml glass bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A 0.05 mm × 12 mm × 50 mm, 99.8% purity aluminum foil piece was rinsed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 11.
[Table 13]

[0091]
  According to Table 11, the data indicate that TMAH may be replaced with various metal ion free bases to increase the aluminum etch rate. To allow removal of metal residues found on the wafer after oxygen plasma ashing in an acceptable stripping temperature and time range, it may be necessary to increase the aluminum etch rate. The data also shows that to obtain the desired aluminum etch rate for the inventive compositions herein,variousConstructionGoldIt indicates that a genus ion-free alkaline component is used.
[0092]
Example 12
The aqueous solution “D1” was prepared by adding 0.14 wt% tetramethylammonium hydroxide (TMAH). The balance of this solution is water (solution pH = 12.3). The aqueous solution “D2” was 0.25 wt% tetramethylammonium hydroxide (TMAH) and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “D3” was 1.2 wt% tetramethylammonium hydroxide (TMAH) and 1.3 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.6). The aqueous solution “D4” was 1.8% by weight tetramethylammonium hydroxide (TMAH) and 2.8% by weight (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.6). Each solution was placed in a 125 ml glass bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A 0.05 mm × 12 mm × 50 mm, 99.8% purity aluminum foil piece was rinsed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 12.
[Table 14]

[0093]
According to Table 12, the data show that the addition of silicate to the metal ion free basic solution inhibits the corrosion of aluminum metal and also obtains the desired aluminum etch rate for the inventive compositions herein. This indicates that metal ion-free silicates added in various concentrations are used.
[0094]
Example 13
The aqueous solution “E1” was 0.22 wt% tetramethylammonium hydroxide (TMAH) and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.2). The aqueous solution “E2” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 2.9 wt% glycerol. The balance of this solution is water (solution pH = 12.1). The aqueous solution “E3” was 0.20 wt% tetramethylammonium hydroxide (TMAH), 0.13 wt% (SiO₂% Conversion) Tetramethylammonium silicate (TMAS) and 9.1 wt% triethylene glycol monomethyl ether were added. The balance of this solution is water (solution pH = 12.2). The aqueous solution “E4” was 0.19 wt% tetramethylammonium hydroxide (TMAH), 0.12 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 13 wt% N-methylpyrrolidinone. The balance of this solution is water (solution pH = 12.2). The aqueous solution “E5” was 0.19 wt% tetramethylammonium hydroxide (TMAH), 0.12 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 17% by weight diethylene glycol. The balance of this solution is water (solution pH = 12.1). The aqueous solution “E6” was 0.17 wt% tetramethylammonium hydroxide (TMAH), 0.11 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 23 wt% isopropyl alcohol. The balance of this solution is water (solution pH = 12.7). Each solution was placed in a 125 ml polyethylene bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A 0.05 mm × 12 mm × 50 mm, 99.8% purity aluminum foil piece was rinsed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 13.
[Table 15]

[0095]
According to Table 13, the data show that the addition of a water-soluble organic solvent is useful to slow the aluminum etch rate. To completely avoid aluminum corrosion during the stripping process, it may be necessary to slow the aluminum etch rate. The aluminum etching rate is inversely proportional to the amount of solvent used, regardless of the solvent type. A wide variety of water soluble solvents are shown below. The data also shows that various types of water-soluble organic solvents are optionally used to obtain the desired aluminum etch rate for the inventive compositions herein.
[0096]
Example 14
The aqueous solution “G1” was 0.22 wt% tetramethylammonium hydroxide (TMAH) and 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.2). The aqueous solution “G2” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 0.10 wt% nonionic surfactant Surfynol-465. The balance of this solution is water (solution pH = 12.2). The aqueous solution “G3” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO₂% Conversion) Tetramethylammonium silicate (TMAS) and 0.10 wt% nonionic surfactant Fluorad FC-170C (product of 3M Industrial Chemicals Division) were added. The balance of this solution is water (solution pH = 12.2). The aqueous solution “G4” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO₂% Conversion) Tetramethylammonium silicate (TMAS) and 0.042 (effective) wt% amphoteric surfactant Reuteric AM KSF-40 (product of Witco Corporation) was added to prepare. The balance of this solution is water (solution pH = 12.2). The aqueous solution “G5” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO₂% Conversion) Tetramethylammonium silicate (TMAS) and 0.026 (effective) wt% anionic surfactant Fluorad FC-93 (a product of 3M Industrial Chemicals Division) was prepared. The balance of this solution is water (solution pH = 12.2). The aqueous solution “G6” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO₂% Conversion) Tetramethylammonium silicate (TMAS) and 0.037 (effective) wt% cationic surfactant Barquat CME-35 (product of Lonza, Inc.) was added. The balance of this solution is water (solution pH = 12.2). Each solution was placed in a 125 ml polyethylene bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A 0.05 mm × 12 mm × 50 mm, 99.8% purity aluminum foil piece was rinsed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 14.
[Table 16]

[0097]
According to Table 14, the data show that the addition of a surfactant is useful to slow the aluminum etch rate. To completely avoid aluminum corrosion during the stripping process, it may be necessary to slow the aluminum etch rate. Useful aluminum etch rate suppression occurs with all four surfactants. This adds to the expected desirable property of improving the wettability of the sample in the presence of a surfactant. The data also indicates that various types of surfactants are optionally used to obtain the desired aluminum etch rate for the inventive compositions herein.
[0098]
Example 15
  Aqueous solution “F1” is 0.20 wt% tetramethylammonium hydroxide (TMAH), 0.11 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA) and 0.07 wt% nonionic interface. Prepared by adding the activator Surfynol-465. The balance of this solution is water (solution pH = 12.3). The aqueous solution “F2” was 0.30% by weight tetramethylammonium hydroxide (TMAH), 0.10% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Tetramethylammonium silicate (TMAS) and 0.07 wt% nonionic surfactant Surfynol-465 were added. The balance of this solution is water (solution pH = 12.3). The aqueous solution “F3” was 0.29% by weight tetramethylammonium hydroxide (TMAH), 0.10% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Tetramethylammonium silicate (TMAS), 3.0 wt% glycerol and 0.07 wt% nonionic surfactant Surfynol-465 were added. The balance of this solution is water (solution pH = 12.1). Sections from the same Si (100) wafer with about 650 nm thermal oxide were rinsed with acetone, dried, and then measured using a Rudolph FTM interferometer to determine the thermal oxide thickness. Four regions were measured and mapped for follow-up measurements after processing. Each sample was then placed in a bottle and again placed in an oven set at 45 ° C. with the lid loosely closed. After 24 hours at about 45 ° C., the bottle was removed from the oven, a sample was removed, washed with water, then rinsed with acetone, dried and further measured with an interferometer. The relative corrosion degree was determined from the difference in the thickness of the thermal oxide film averaged over the four regions on the sample. The results are shown in Table 15.
[Table 17]

[0099]
  According to Table 15, data accompanies exposure to alkaline solutiontwoIt shows that the addition of silicate is advantageous to prevent or weaken the corrosion of silicon oxide. Typically, the silicon dioxide dielectric is present on the surface of the integrated circuit during metal wiring or bias stripping. Damage to these dielectrics must be avoided. The data also shows that the addition of tetramethylammonium silicate to a tetramethylammonium hydroxide-based cleaning solution typically inhibits unwanted corrosion of dielectric materials present in integrated circuits.
[0100]
Example 16
Organic contaminants remaining after washing were measured using a secondary ion mass spectrometer (SIMS). A silicon wafer sample sputtered with a 0.35 micron film of aluminum-1% copper alloy is treated with a silicate solution “A” and a commercially available post-etch residue remover, EKC-265.^TMAlso washed (product of EKC Technology, Inc.). EKC-265^TMComprises about 15% to 20% of catechol, hydroxylamine and water, respectively, with the balance being 2- (2-aminoethoxy) ethanol. The wafer sample was placed in solution “A” at 35 ° C. for 5 minutes, then rinsed with deionized water filtered at 0.2 microns for 2 minutes and dried under pressure nitrogen. A second wafer sample is prepared using EKC-265 using the time and temperature recommended by the manufacturer.^TMTreated in the same way. A third untreated wafer piece (also from the same silicone wafer) was used as a control. The wafer samples were then analyzed by Dynamic-SIMS using an etch rate of 22.1 Å / sec with a 0.5 second pause. The carbon surface contamination of the three samples was then compared using the carbon-12 atomic power released from the surface. The results are shown in Table 16.
[Table 18]

[0101]
According to Table 16, the data show the advantages of the present invention with respect to providing a surface free of organic contaminants after cleaning, and the use of the composition described herein for integrated circuits with carbon-containing (organic) impurities. Indicates that there is almost no contamination.
[0102]
Example 17
  Aqueous solution “H1” is 0.27 wt% tetramethylammonium hydroxide (TMAH), 0.092 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.062 wt% nonionic interface Activator Surfynol-465, 0.13% by weight (Si0₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 2.7 wt% glycerol. The balance of this solution is water. Aqueous solution “H2” is 0.28 wt% tetramethylammonium hydroxide (TMAH), 0.097 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.065 wt% nonionic interface Activator Surfynol-465, 0.13% by weight (Si0₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 2.9 wt% glycerol. The balance of this solution is water. Aqueous solution “H3” is 0.32 wt% tetramethylammonium hydroxide (TMAH), 0.11 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.075 wt% nonionic interface Activator Surfynol-465, 0.15% by weight (Si0₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 3.3 wt% glycerol. The balance of this solution is water. Aqueous solution “H4” is 0.39 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.091 wt% nonionic interface Activator Surfynol-465, 0.19 wt% (Si0₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 4.0 wt% glycerol. The balance of this solution is water. Aqueous solution “H5” is 0.58 wt% tetramethylammonium hydroxide (TMAH), 0.20 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.14 wt% nonionic interface Activator Surfynol-465, 0.28 wt% (Si0₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 6.0 wt% glycerol. The balance of this solution is water. Aqueous solution “H6” is 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.41 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.27 wt% nonionic interface. Activator Surfynol-465, 0.56% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 12 wt% glycerol were added. The balance of this solution is water. The aqueous solution “H7” was 5.1 wt% tetramethylammonium hydroxide (TMAH), 1.8 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 2.4 wt% (SiO₂% Conversion) Tetramethylammonium silicate (TMAS) and 52 wt% glycerol were added. The balance of this solution is water. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Wafer # 5 and # 6 samples with 1 micron wide undulations and wiring made of aluminum copper and capped with titanium nitride, previously removed by removing organic photoresist residues, while leaving behind mainly inorganic residues Was used to evaluate the performance of the solution. Wafer samples # 7 and # 8 having a width of 1/2 micron with respect to a 1 micron deep hole (bias) through the dielectric material exposing the aluminum copper metal on its substrate are (a) aluminum copper, then Plating with titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a lithographic pattern of bias using a photoresist material, and (d) patterning using reactive ion etching. Transferred to the dielectric layer and (e) pre-manufactured by removing most of the remaining photoresist by oxygen plasma ashing, while mainly leaving behind inorganic residues. Wafer sample # 9, having a width of 1 micron against a 1 micron deep tapered hole (bias) through the dielectric material exposing the aluminum copper metal on its substrate, is plated with (a) aluminum copper and then titanium nitride. (B) coated with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using photoresist material, and (d) transferring the pattern to the dielectric layer using reactive ion etching And (e) pre-manufactured by removing most of the remaining photoresist by oxygen plasma ashing, while mainly leaving behind inorganic residues. Wafer samples were removed from the solution at 21-45 ° C. for 5-10 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Tables 17A to 17E.
[Table 19]

[Table 20]

[Table 21]

[Table 22]

[Table 23]

[0103]
According to Tables 17A through 17E, the data was obtained from several different oxygen plasma ashed wafer samples with seven different formulations and no unacceptable aluminum corrosion by varying the pH and concentration of each component. This shows that the residue can be cleaned well.
[0104]
Example 18
  The aqueous solution “H8” was 5.1% by weight tetramethylammonium hydroxide (TMAH), 1.8% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 2.4% by weight (SiO₂% Conversion) Tetramethylammonium silicate (TMAS) and 52 wt% dimethyl sulfoxide (DMSO) were added. The balance of this solution is water. Aqueous solution “H9” is 0.58 wt% tetramethylammonium hydroxide (TMAH), 0.20 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.14 wt% nonionic interface Activator Surfynol-465, 0.28 wt% (Si0₂% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 6.0 wt% glycerol. The balance of this solution is water. Aqueous solution “H10” is 0.88 wt% tetramethylammonium hydroxide (TMAH), 0.30 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.20 wt% nonionic interface Activator Surfynol-465, 0.42% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 9.0 wt% glycerol were added. The balance of this solution is water. Wafer sample # 10, having a width of 1 micron for a 2 micron deep hole (bias) through the dielectric material exposing the photoresist and aluminum copper metal on its substrate, is: (a) aluminum copper, then titanium nitride (B) coated with a silicon oxide dielectric using chemical vapor deposition, (c) a lithographic pattern of bias using a layer of photoresist material about 1 micron thick, and (d) reactive ions. The pattern was transferred to the dielectric layer using etching, and (e) pre-manufactured by removing the solvent by hard baking of the photoresist at high temperature, while leaving behind mainly the organic photoresist layer. Using this sample, the performance of the solution was evaluated as follows. The wafer sample was removed from the solution at 45-65 ° C. for 20-30 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the samples were observed with a scanning electron microscope (SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 18.
[Table 24]

[0105]
According to Table 18, the data demonstrates the ability of the present invention to clean the organic photoresist layer from the semiconductor wafer surface before the sample is oxygen plasma ashed, while preventing or reducing the corrosion of aluminum undulations. Yes.
[0106]
Example 19
The aqueous solution “H11” was 6.2% by weight tetramethylammonium hydroxide (TMAH), 2.1% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 64% by weight glycerol and 2.9%. % By weight (Si0₂% Conversion) prepared by adding a colloidal silica solution (having a particle size of 20 nm). The balance of this solution is water. The pH of the solution “H11” is about 13.1. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Wafer samples # 5 and # 6 having 1 micron wide reliefs and wirings formed of aluminum copper and capped with titanium nitride, previously removed by removing organic photoresist residues, while leaving mainly inorganic residues behind Was used. Treatment for each sample was performed at 22-45 ° C. for 5-10 minutes, removed, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are similar to those obtained for solution “H7” in Example 17, indicating that colloidal silica can be used as a source of silicates free of water-soluble metal ions of the present invention.
[0107]
Example 20
Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water, and this pH is about 12.1. The aqueous solution “Z” was prepared by adding 1.3 wt% tetramethylammonium hydroxide (TMAH), 0.58 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) The balance is water), and the pH is about 13.0. The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO₂% Conversion) Prepared using tetramethylammonium silicate (TMAS) 18.5% by weight hydroxylamine and 0.07% by weight nonionic surfactant Surfynol-465 (the remainder of the solution is water), the pH is about 12 .1. The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 22-65 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 19.
[Table 25]

[0108]
According to Table 19, the data show the ability of hydroxylamine or hydrogen peroxide to facilitate the removal of titanium-containing residues at low temperatures.
[0109]
Example 21
The aqueous solution “M2” was 0.67% by weight tetramethylammonium hydroxide (TMAH), 0.46% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) prepared using tetramethylammonium silicate (TMAS), 1.0 wt% hydroxylamine and 0.07 wt% nonionic surfactant Surfynol-465 (the rest of the solution is water), the pH is about 12.1. The aqueous solution “M3” was 0.94 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.20 wt% (SiO₂% Conversion) prepared using tetramethylammonium silicate (TMAS), 5.1 wt% hydroxylamine and 0.1 wt% nonionic surfactant Surfynol-465 (the remainder of the solution is water), and the pH is about 12 .1. The aqueous solution “M4” was 1.1 wt% tetramethylammonium hydroxide (TMAH), 0.46 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.18 wt% (SiO₂% Conversion) prepared using tetramethylammonium silicate (TMAS), 10.0 wt% hydroxylamine and 0.09 wt% nonionic surfactant Surfynol-465 (the rest of the solution is water), the pH is about 12.1. The aqueous solution “M5” was 1.3% by weight tetramethylammonium hydroxide (TMAH), 0.42% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 47.3 wt% hydroxylamine (the remainder of the solution is water), the pH is about 12.1. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 35 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 20.
[Table 26]

[0110]
According to Table 20, the data show the ability of hydroxylamine to facilitate the removal of titanium-containing residues at low temperatures.
[0111]
Example 22
The aqueous solution “M6” was 0.82 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO₂% Conversion) prepared using tetramethylammonium silicate (TMAS), 18.8 wt% hydroxylamine and 0.07 wt% nonionic surfactant Surfynol-465 (the balance of this solution is water), and this pH is about 12.1. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 35 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 21.
[Table 27]

[0112]
According to Table 21, the data show that good stripping performance is obtained over a range of CyDTA concentrations. Thus, the amount of chelating agent present can be adjusted to accommodate the sample being washed. More difficult samples may require this desired component to achieve complete washing. The data also indicates that chelating agents are optionally used in the compositions disclosed herein.
[0113]
Example 23
The aqueous solution “M7” was 6.0 wt% tetramethylammonium hydroxide (TMAH), 0.35 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 1.2 wt% (SiO₂% Conversion) prepared using tetramethylammonium silicate (TMAS), 17.7 wt% hydroxylamine and 0.06 wt% nonionic surfactant Surfynol-465 (the remainder of the solution is water), and the pH is about 13.0. The aqueous solution “M8” was 7.1 wt% tetramethylammonium hydroxide (TMAH), 0.46 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 2.7 wt% (SiO₂% Conversion) Prepared using tetramethylammonium silicate (TMAS) and 19.1% by weight hydroxylamine (the remainder of the solution is water), the pH is about 13.0. The aqueous solution “M9” was 8.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 4.1 wt% (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 19.0 wt% hydroxylamine (the remainder of the solution is water), the pH is 13.0. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 35 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 22.
[Table 28]

[0114]
According to Table 22, the data show the ability of tetramethylammonium silicate to prevent or attenuate corrosion of exposed aluminum on the base of the bias even at very high formulation pH.
[0115]
Example 24
The aqueous solution “M10” was 0.34 wt% tetramethylammonium hydroxide (TMAH), 0.47 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.01 wt% (SiO₂% Conversion) prepared using tetramethylammonium silicate (TMAS), 18.6% by weight hydroxylamine and 0.06% by weight nonionic surfactant Surfynol-465 (the remainder of the solution is water), and the pH is about 10.1. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 20-65 ° C. for 5-30 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 23.
[Table 29]

[0116]
According to Table 23, the data show that high pH, high concentration of tetramethylammonium silicate can be used to inhibit aluminum corrosion. The data also shows that high pH, low working temperature can be used.
[0117]
Example 25
The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. The aqueous solution “P2” was 9.7 wt% tetramethylammonium hydroxide (TMAH), 0.11 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 9.4 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 21-35 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 24.
[Table 30]

[0118]
According to Table 24, the data show that a range of hydrogen peroxide concentrations are useful for removing titanium-containing residues in the bias.
[0119]
Example 26
The aqueous solution “P3” was 3.5% by weight tetramethylammonium hydroxide (TMAH), 0.10% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.5 wt% hydrogen peroxide (the remainder of the solution is water), and the pH is about 12.2. The aqueous solution “P4” was 3.9 wt% tetramethylammonium hydroxide (TMAH), 0.096 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.59 wt% (SiO₂% Conversion) prepared with tetramethylammonium silicate (TMAS) and 1.4 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 12.2. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 22 ° C. for 10 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 25.
[Table 31]

[0120]
According to Table 25, the data show that high concentrations of tetramethylammonium silicate can be used to inhibit aluminum corrosion when hydrogen peroxide is present.
[0121]
Example 27
The aqueous solution “P5” was 2.1 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO₂% Conversion) prepared with tetramethylammonium silicate (TMAS) and 1.5 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. The aqueous solution “P6” was 2.4% by weight tetramethylammonium hydroxide (TMAH), 0.53% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. The aqueous solution “P7” was 2.9 wt% tetramethylammonium hydroxide (TMAH), 1.4 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO₂% Conversion) prepared with tetramethylammonium silicate (TMAS) and 1.5 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 21-23 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 26.
[Table 32]

[0122]
According to Table 26, the data indicate that a range of CyDTA concentrations are useful.
[0123]
Example 28
  The aqueous solution “P8” was 0.40 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO₂% Conversion) prepared using tetramethylammonium silicate (TMAS) and 19.2 wt% hydrazine (the remainder of the solution is water), the pH is about 12.1. The aqueous solution “P9” was 4.33 wt% tetramethylammonium hydroxide (TMAH), 0.088 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.12 wt% (SiO₂% Conversion) Prepared using tetramethylammonium silicate (TMAS) and 15.7 wt% formaldehyde (the remainder of the solution is water), the pH is about 12.1. The aqueous solution “P10” was 0.26 wt% tetramethylammonium hydroxide (TMAH), 11.5 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.13 wt% (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 16.7 wt% methylamine (the remainder of the solution is water) and the pH is about 12.1. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 35 ° C. for 20-30 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 27.
[Table 33]

[0124]
According to Table 27, the data show that other small molecules have no effect on titanium residue removal. Like hydroxylamine, hydrazine is a powerful reducing agent. It is not anticipated that hydrazine will be ineffective, and using a silicate-containing formulation, the titanium-containing residue found in wafer sample # 11 can be cleaned from bias, which is unique to hydroxylamine and hydrogen peroxide. It proves that it is a thing.
[0125]
Example 29
  Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Surfactol-465, 0.14% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water and the pH is about 12.1. The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO₂%) Prepared using tetramethylammonium silicate (TMAS), 18.5 wt% hydroxylamine and 0.07 wt% nonionic surfactant Surfynol-465 (the balance of this solution is water) About 12.1. The aqueous solution “P8” was 0.40 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO₂% Conversion) prepared using tetramethylammonium silicate (TMAS) and 19.2 wt% hydrazine (the remainder of the solution is water), the pH is about 12.1. Aqueous solution “S1” was 583 grams deionized water, 7.8 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 8.6 grams tetramethylammonium silicate (TMAS, SiO₂As the pH is 12.5. Aqueous solution “S2” was prepared by combining 99.0 grams of solution “S1” with 2.5 grams of β-cyclodextrin (solution pH = 12.1). Aqueous solution “S3” was prepared by combining 99.0 grams of solution “S1” with 2.5 grams of sodium hypophosphite (solution pH = 12.3). Aqueous solution “S4” was prepared by combining 99.0 grams of solution “S1” with 2.5 grams of sodium dithionite (solution pH = 6.7). Aqueous solution “S5” was prepared by combining 99.0 grams of solution “S1” with 2.5 grams of sodium sulfite (solution pH = 12.3). The stock aqueous solution “S5b” is 1,775.2 grams deionized water and 96.0 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution, 8.8 grams trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid. (CyDTA) and 114.8 grams tetramethylammonium silicate (TMAS, SiO)₂As 10.0%). Preservative aqueous solution “S5c” consists of 900 ml deionized water and 300 ml solution “S5”.bIt was prepared by combining. Aqueous solution “S6” was prepared by combining 80.0 grams solution “S5c”, 5.0 grams L-ascorbic acid and 18.2 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution (solution pH = 12). .3). Aqueous solution “S7” was prepared by combining 80.0 grams of solution “S5c”, 5.0 grams of hydroquinone and 27.1 grams of tetramethylammonium hydroxide (TMAH) 25% aqueous solution (solution pH = 12.4). . Aqueous solution “S8” was prepared by combining 80.0 gram solution “S5c”, 5.0 gram L (+)-cysteine and 29.6 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution (solution pH). = 12.4). Aqueous solution “S9” was prepared by combining 80.0 grams solution “S5c”, 10.0 grams ammonium persulfate and 32.9 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution (solution pH = 12.6). ). Aqueous solution “S10” was prepared by combining 80.0 grams of solution “S5c”, 5.0 grams of nitric acid and 10.2 grams of tetramethylammonium hydroxide pentahydrate (TMAH) (solution pH = 12.4). ). Aqueous solution “S11” was prepared by combining 90.0 grams of solution “S5c”, 5.0 grams and 19.2 grams of 25% aqueous solution of tetramethylammonium hydroxide (TMAH) (solution pH = 12.3). Aqueous solution “S12” was 80.0 grams solution “S5c”, 5.0 grams 88% formic acid, 10.0 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 12.7 grams tetramethylammonium hydroxide pentahydrate. (TMAH) was prepared by combining (solution pH = 12.6). Aqueous solution “S13” was prepared by combining 80.0 grams of solution “S5c”, 5.0 grams of sulfuric acid and 17.5 grams of tetramethylammonium hydroxide pentahydrate (TMAH) (solution pH = 12.3). ). Aqueous solution “S14” was prepared by combining 80.0 grams of solution “S5c”, 5.0 grams of phosphoric acid and 20.1 grams of tetramethylammonium hydroxide pentahydrate (TMAH) (solution pH = 12 .3). Aqueous solution “S15” is 80.0 grams solution “S5c”, 6.0 grams oxalic acidtwoPrepared by combining hydrate, 16.0 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 9.3 grams tetramethylammonium hydroxide pentahydrate (TMAH) (solution pH = 12.6). ). Aqueous solution “S16” was prepared by combining 80.0 grams solution “S5c”, 5.0 grams catechol and 16.1 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution (solution pH = 12.4). . Each solution was placed in a 125 ml polyethylene bottle and placed in an oven set at 45 ° C. with the lid tightly closed and preheated for 1 hour. A 0.025 mm × 13 mm × 50 mm, 99.94% pure titanium foil piece was rinsed with deionized water, acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of titanium foil was placed in a jar, re-capped and returned to the oven. After 24 hours at about 45 ° C., the bottle was removed from the oven. The titanium foil pieces were removed and rinsed with deionized water, then with acetone, dried and weighed on a chemical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 28.
[Table 34]

[0126]
According to Table 28, the data indicate that all of the possible titanium residue removal accelerators tested above (except hydroxyamine) were ineffective at process temperatures as low as 45 ° C. The lack of effectiveness of the hydrazine shown here confirms the FE-SEM results shown in Example 28. The results shown demonstrate that it is peculiar to hydroxylamine to increase the relative titanium etch (removal) rate.
[0127]
Example 30
  The aqueous solution “R1” was 583 grams deionized water, 4.68 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 8.64 grams tetramethylammonium silicate (TMAS, SiO).₂As 10.0%) and 0.66 grams trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), which has a pH of 11.3. Aqueous solution “R2” was prepared by combining 99.0 gram solution “R1”, 0.33 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 1.0 gram hydroxylamine 50% aqueous solution (solution pH = 12.0). Aqueous solution “R3” was prepared by combining 99.0 gram solution “R1”, 0.34 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 5.0 gram hydroxylamine 50% aqueous solution (solution pH = 11.9). Aqueous solution “R4” was prepared by combining 99.0 gram solution “R1”, 0.34 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 10.0 gram hydroxylamine 50% aqueous solution (solution pH = 11.6). Aqueous solution “R5” was prepared by combining 99.0 gram solution “R1”, 0.52 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 1.0 gram hydroxylamine 50% aqueous solution (solution pH = 12.2). Aqueous solution “R6” was prepared by combining 99.0 gram solution “R1”, 0.54 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 5.0 gram hydroxylamine 50% aqueous solution (solution pH = 12.0). Aqueous solution “R7” was prepared by combining 99.0 grams of solution “R1”, 0.56 grams of tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 10.2 grams hydroxylamine 50% aqueous solution (solution pH = 11.8). The stock aqueous solution “R8” is 583 grams deionized water, 4.68 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 8.64 grams tetramethylammonium silicate (TMAS, SiO).₂As the pH is 12.0. Aqueous solution “R9” was prepared by combining 94.0 grams solution “R8” and 20.0 grams hydroxylamine 50% aqueous solution (solution pH = 11.3). Each solution was placed in a 125 ml polyethylene bottle and placed in an oven set at 45 ° C. with the lid tightly closed and preheated for 1 hour. A 0.025 mm × 13 mm × 50 mm, 99.94% pure titanium foil piece was rinsed with deionized water, acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of titanium foil was placed in a jar, re-capped and returned to the oven. After 24 hours at about 45 ° C., the bottle was removed from the oven. The titanium foil pieces were removed and rinsed with deionized water, then with acetone, dried and weighed on a chemical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 29.
[Table 35]

[0128]
According to Table 29, the data indicate that as the concentration of the titanium residue removal accelerator hydroxylamine increases, the relative titanium foil removal increases. The degree of titanium removal in this test is directly proportional to the effectiveness in cleaning wafer sample # 11.
[0129]
Example 31
The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO₂% Conversion) Prepared using tetramethylammonium silicate (TMAS) 18.5% by weight hydroxylamine and 0.07% by weight nonionic surfactant Surfynol-465 (the remainder of the solution is water), the pH is about 12 .1. The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. The commercially available post-etch residue remover used for comparison is EKC-265.^TM(Product of EKC Technology, Inc.) and ACT-935TM (product of ACT Inc.). Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 35 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 30.
[Table 36]

[0130]
According to Table 30, the data show that at a process temperature as low as 35 ° C., the composition of the present invention was effective in removing residues known to contain titanium. This data also shows that the use of the titanium residue removal accelerator hydroxylamine for low temperature cleaning is unique to the compositions of the present invention.
[0131]
Example 32
Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water, and this pH is about 12.1. The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO₂% Conversion) Prepared using tetramethylammonium silicate (TMAS) 18.5% by weight hydroxylamine and 0.07% by weight nonionic surfactant Surfynol-465 (the remainder of the solution is water), the pH is about 12 .1. The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. A silicone wafer sample with a cured layer of hydrogen silsesquioxane (HSQ) low-k dielectric was placed in a Fourier transform infrared (FTIR) spectrometer and a reference spectrum was taken. HSQ has Si—H bonds in its structure, which is 2100 cm.^-1It is clear that The wafer sample was then processed in one of the above solutions at room temperature (about 22 ° C.) for 10 minutes, rinsed with deionized water and further dried. The sample was then placed in FTIR and a second spectrum was obtained. About 2100cm^-1Were used to compare the processed wafer spectra against the reference spectra. For comparison, a commercially available post-etch residue remover, EKC-265^TM(Product of EKC Technology, Inc.) was similarly tested (10 minutes) at the manufacturer's recommended temperature of 65 ° C. The results are shown in Table 31.
[Table 37]

[0132]
According to Table 31, the data show that the compositions of the present invention are unique in that they are compatible with photosensitive low-k dielectric materials such as HSQ.
[0133]
Example 33
  Aqueous solution “A” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 (product of Air Products and Chemicals, Inc.) and 0.14% by weight (SiO₂% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 12.2. Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water, and this pH is about 12.1. The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO₂% Conversion) Prepared using tetramethylammonium silicate (TMAS) 18.5% by weight hydroxylamine and 0.07% by weight nonionic surfactant Surfynol-465 (the remainder of the solution is water), the pH is about 12 .1. The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. Storage aqueous solution “T1” is 1.6 wt% tetramethylammonium hydroxide (TMAH), 0.41 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.27 wt% nonionic Surfactant Surfynol-465, 0.56% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 12 wt% glycerol were added. The balance of the solution is water, and the pH is about 12.5. Aqueous solution “T2” was prepared by diluting 25 ml solution “T1” with 70 ml deionized water and 5 ml glycerol. Aqueous solution “T3” was prepared by diluting 25 ml solution “T1” with 65 ml deionized water and 10 ml glycerol. Aqueous solution “T4” was prepared by diluting 25 ml solution “T1” with 60 ml deionized water and 15 ml glycerol. Aqueous solution “T5” was prepared by diluting 25 ml solution “T1” with 55 ml deionized water and 20 ml glycerol. Aqueous solution “T6” was prepared by diluting 25 ml solution “T1” with 50 ml deionized water and 25 ml glycerol. Aqueous solution “T7” was prepared by diluting 25 ml solution “T1” with 25 ml deionized water and 50 ml glycerol. Aqueous solution “T8” was prepared by diluting 25 ml solution “T1” with 75 ml glycerol. Aqueous solution “T9” was prepared by diluting 25 ml solution “T1” with 70 ml deionized water and 5 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T10” was prepared by diluting 25 ml solution “T1” with 65 ml deionized water and 10 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T11” was prepared by diluting 25 ml solution “T1” with 60 ml deionized water and 15 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T12” was prepared by diluting 25 ml solution “T1” with 55 ml deionized water and 20 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T13” was prepared by diluting 25 ml solution “T1” with 50 ml deionized water and 25 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T14” was prepared by diluting 25 ml solution “T1” with 25 ml deionized water and 50 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T15” was prepared by diluting 25 ml solution “T1” with 75 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Each solution was placed in a 125 ml polyethylene bottle, tightly capped and placed in an oven set at 45 ° C, 65 ° C or 85 ° C and preheated for 1 hour or held at room temperature (about 22 ° C). A piece of 0.025 mm × 13 mm × 50 mm pure copper foil was immersed in dilute hydrochloric acid, rinsed with deionized water and acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven (if heated), and then a piece of copper foil was placed in a jar and again capped and returned to the oven. After 24 hours at about 22-85 ° C., the bottle was removed from the oven. A piece of copper foil was removed, rinsed with deionized water, then with acetone, dried and weighed on a chemical balance. The degree of corrosion was determined from the weight loss. For comparison, a commercially available post-etch residue remover, EKC-265^TM(Product of EKC Technology, Inc.), EKC-270^TM(Product of EKC Technology, Inc.), EKC-311^TM(Product of EKC Technology, Inc.), ACT-935TM (product of ACT Inc.), ACT NP-937^TM(ACT Inc. product) and ACT-941TM (ACT Inc. product) were similarly tested at the manufacturer's recommended temperature of 65 ° C. The results are shown in Table 32.
[Table 38]

[0134]
According to Table 32, the data show that several compositions of the present invention are compatible with copper. The data also shows that the composition M1 of the present invention is superior to a commercially available hydroxylamine-containing post-etch residue remover formulation for use with copper plating. Furthermore, the data show that the addition of the titanium residue removal accelerator hydrogen peroxide reduces the copper corrosion rate.
[0135]
Example 34
Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water, and this pH is about 12.1. In a clean room, the total particles found on a 3 inch silicone wafer with 650 angstroms of thermal oxide were measured using a wafer particle counter (size of 0.1 to 10 microns). The wafer was then chemically mechanically polished (CMP) with an alumina-based polishing slurry and rinsed with deionized water. The wafer was then “brush cleaned” using solution “L” at room temperature (about 22 ° C.), then rinsed with deionized water and spin-dried. The total particle (0.1 to 10 micron size) present on the wafer surface after cleaning was then measured using a wafer particle counter. For comparison, a second wafer using deionized water as a “brush cleaner” after CMP was tested. The results are shown in Table 33.
[Table 39]

[0136]
According to Table 33, the data show that the compositions of the present invention are unique because they remove particulate contaminants that occur after chemical mechanical polishing.
[0137]
Example 35
Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si0₂% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water, and this pH is about 12.1. The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO₂% Conversion) prepared using tetramethylammonium silicate (TMAS), 18.5 wt% hydroxylamine and 0.07 wt% nonionic surfactant Surfynol-465 (the remainder of the solution is water), and the pH is about 12.1. The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO₂% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. Sections from the same Si (100) wafer with about 650 nm thermal oxide were rinsed with acetone, dried, and further measured with a Rudolph FTM interferometer to determine the thermal oxide thickness. Four ranges were measured and mapped for follow-up measurements after processing. Each sample was then placed in a jar and again loosely capped and placed in an oven pre-set at 45 ° C. or left at room temperature (about 22 ° C.). After 24 hours at about 22 ° C. or about 45 ° C., the bottle was removed from the oven and the sample was removed, washed with water, then rinsed with acetone, dried and measured with an interferometer. The relative etch rate was determined from the difference in the thickness of the thermal oxide film averaged over the four areas on the sample. For comparison, a commercially available post-etch residue remover, EKC-265^TM(Product of EKC Technology, Inc.), EKC-270^TM(Product of EKC Technology, Inc.), EKC-311^TM(Product of EKC Technology, Inc.), ACT-935^TM(Product of ACT Inc.), ACT NP-937^TM(A product of ACT Inc.) and ACT-941^TM(ACT Inc. product) was similarly tested at the manufacturer's recommended temperature of 65 ° C. The results are shown in Table 34.
[Table 40]

* 18 hours test at 65 ℃
[0138]
According to Table 34, the data show that the compositions of the present invention are unique in that they clean unwanted residues from the wafer substrate without undesirable etching of the dielectric layer. These results are consistent with the results shown in Example # 15 for silicate-containing compositions.
[0139]
The examples show 10 surprising and unexpected results related to the present invention. First, it is possible to clean undesirable residues from the wafer surface while preventing undesirable metal corrosion at low working temperatures and short working times. Second, the use of silicate as a buffer, high dilution rate, and unexpectedly high bath stability of the high pH composition (pKa = 11.8). Third, the silicate added to the highly alkaline cleaning agent inhibits undesirable dissolution of the silicon oxide dielectric material present in the integrated circuit. Fourth, because the composition is very aqueous (typically> 80% water), no intermediate rinsing step is required prior to water washing to prevent post-wash corrosion. Fifth, due to the high moisture content of these compositions, the hygiene, safety, and environmental health associated with use and handling compared to typical organic photoresist strippers and post-plasma ash residue removers. The risk of Sixth, the composition of the present invention has been shown to have substantially no carbon residue contamination on the substrate surface after processing compared to a typical post-organic ash residue remover. . Seventh, it has been found that the compositions of the present invention are compatible with photosensitive low-k dielectric materials used in integrated circuits. Eighth, it is possible to remove difficult-to-handle titanium-containing residues at low temperatures. Ninth, it has been found that the composition of the present invention is compatible with copper metal. Tenth, it has been found that the compositions of the present invention are also effective in removing silica and alumina chemical mechanical polishing (CMP) slurry residues from wafer substrates. Silicates are known aluminum corrosion inhibitors, but their ability to inhibit aluminum corrosion and to selectively remove high aluminum and / or titanium content metal-containing photoresist residues is surprising. Yes and unexpected. Silicate buffering during processing, negligible carbon contamination on substrate surface, low dielectric etch, compatibility with photosensitive low-k dielectric materials, compatibility with copper metal, low-handling titanium-containing residues at low temperatures The ability to be removed, the ability to clean silica and alumina chemical mechanical polishing (CMP) slurry residues and the ability to effectively use such high water concentrations were also surprising and unexpected aspects of the present invention.
[0140]
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. Accordingly, it is to be understood that the invention may be practiced otherwise than as specifically described within the scope of the appended claims.

Claims (26)

A composition for stripping or cleaning an integrated circuit substrate containing a titanium residue, comprising :
(A) one or more metal ion free bases selected from the group consisting of quaternary ammonium hydroxide, ammonium hydroxide and organic amines in an amount sufficient to provide a pH 11 or higher solution;
(B) a water-soluble metal ion-free silicate selected from the group consisting of 0.01 wt% to 5 wt% ammonium silicate and quaternary ammonium silicate;
(C) (1) 0.01% to 10% by weight of (ethylenedinitrilo) tetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N 1, selected from the group consisting of ', N'-tetraacetic acid, N, N, N', N'-ethylenediaminetetra (methylene phosphoric acid), and (1,2-cyclohexylenedinitrilo) -tetraacetic acid or One or more chelating agents, or (2) one or more titanium residue removal accelerators selected from the group consisting of 1 wt% to 50 wt% hydroxylamine, hydroxylamine salt, peroxide, ozone and fluoride At least one component comprising either or both of
(D) A composition comprising water.   The composition of claim 1, wherein the metal ion free base is present in an amount sufficient to provide a pH of 11-13.   The composition of claim 1 further comprising one or more water-soluble auxiliary organic solvents.   The composition according to claim 3, wherein the concentration of the water-soluble auxiliary organic solvent is 0.1 wt% to 80 wt%.   5. The composition of claim 4, wherein the water soluble auxiliary organic solvent is selected from the group consisting of 1-hydroxyalkyl-2-pyrrolidinone, alcohols and polyhydroxy compounds.   The composition of claim 1, further comprising one or more water-soluble surfactants.   The composition according to claim 6, wherein the concentration of the water-soluble surfactant is 0.01% by weight to 1% by weight.   The composition of claim 1, wherein the base is selected from the group consisting of choline, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, methyltriethanolammonium hydroxide, and methyltriethylammonium hydroxide.   The composition according to claim 1, wherein the water-soluble metal ion-free silicate is tetramethylammonium silicate.   The composition according to claim 1, comprising from 0.1 to 3% by weight of tetramethylammonium hydroxide and from 0.01 to 1% by weight of tetramethylammonium silicate.   The composition according to claim 10, further comprising 0.01 to 1% by weight of trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid. A method for cleaning a semiconductor wafer substrate containing a titanium residue ,
A semiconductor wafer substrate at a time and temperature sufficient to clean undesired contaminants and residues from the substrate surface;
(A) one or more metal ion free bases selected from the group consisting of quaternary ammonium hydroxide, ammonium hydroxide and organic amines in an amount sufficient to provide a pH 11 or higher solution;
(B) a water-soluble metal ion-free silicate selected from the group consisting of 0.01 wt% to 5 wt% ammonium silicate and quaternary ammonium silicate;
(C) (1) 0.01% to 10% by weight of (ethylenedinitrilo) tetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N 1, selected from the group consisting of ', N'-tetraacetic acid, N, N, N', N'-ethylenediaminetetra (methylene phosphoric acid), and (1,2-cyclohexylenedinitrilo) -tetraacetic acid or One or more chelating agents, or (2) one or more titanium residue removal accelerators selected from the group consisting of 1 wt% to 50 wt% hydroxylamine, hydroxylamine salt, peroxide, ozone and fluoride At least one component comprising either or both of
(D) A method comprising contacting with a composition comprising water.   The method of claim 12, wherein the semiconductor wafer substrate is contacted with the composition for 1 to 30 minutes.   The method of claim 12, wherein the semiconductor wafer substrate is contacted with the composition at a temperature of 10 ° C. to 85 ° C.   The method of claim 12, further comprising rinsing and drying steps.   13. The method of claim 12, wherein the composition contains metal ion free base in an amount sufficient to bring the pH to 11-13.   13. The method of claim 12, further comprising one or more water-soluble auxiliary organic solvents in the composition.   The process according to claim 17, wherein the concentration of the water-soluble auxiliary organic solvent is from 0.1% to 80% by weight.   18. The method of claim 17, wherein the water soluble auxiliary organic solvent is selected from the group consisting of 1-hydroxyalkyl-2-pyrrolidinone, alcohols and polyhydroxy compounds.   13. The method of claim 12, further comprising one or more water soluble surfactants in the composition.   The method according to claim 20, wherein the concentration of the water-soluble surfactant is 0.01% by weight to 1% by weight.   13. The method of claim 12, wherein the base in the composition is selected from the group consisting of choline, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, methyltriethanolammonium hydroxide, and methyltriethylammonium hydroxide.   The method according to claim 12, wherein the water-soluble metal ion-free silicate in the composition is tetramethylammonium silicate.   The process according to claim 12, wherein the composition comprises 0.1 to 3 wt% tetramethylammonium hydroxide and 0.01 to 1 wt% tetramethylammonium silicate.   25. The method of claim 24, wherein the composition further comprises 0.01 to 1% by weight of trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid. (A) one or more metal ion free bases selected from the group consisting of quaternary ammonium hydroxide, ammonium hydroxide and organic amines in an amount sufficient to provide a pH 11 or higher solution;
(B) a water-soluble metal ion-free silicate selected from the group consisting of 0.01 wt% to 5 wt% ammonium silicate and quaternary ammonium silicate;
(C) (1) 0.01% to 10% by weight of (ethylenedinitrilo) tetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N 1, selected from the group consisting of ', N'-tetraacetic acid, N, N, N', N'-ethylenediaminetetra (methylene phosphoric acid), and (1,2-cyclohexylenedinitrilo) -tetraacetic acid or One or more chelating agents, or (2) one or more titanium residue removal accelerators selected from the group consisting of 1 wt% to 50 wt% hydroxylamine, hydroxylamine salt, peroxide, ozone and fluoride At least one component comprising either or both of
(D) A composition for stripping or cleaning an integrated circuit substrate containing a titanium residue formed by mixing water.