JP2009540581A - 汚染および表面分解を最小限に抑えるための層間絶縁膜の表面改質 - Google Patents
汚染および表面分解を最小限に抑えるための層間絶縁膜の表面改質 Download PDFInfo
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- JP2009540581A JP2009540581A JP2009514560A JP2009514560A JP2009540581A JP 2009540581 A JP2009540581 A JP 2009540581A JP 2009514560 A JP2009514560 A JP 2009514560A JP 2009514560 A JP2009514560 A JP 2009514560A JP 2009540581 A JP2009540581 A JP 2009540581A
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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Abstract
【解決手段】半導体システムは、誘電体層(104)を提供することと、誘電体層(104)内に、誘電体層(104)の上部に露出される導体(108)を提供することと、露出された導体(108)をキャッピングすることと、誘電体層(104)の表面を改質することであって、導体(108)を低pH溶液に溶解させて誘電体層(104)から導体(108)イオンを洗浄すること、導体(108)イオン下方の誘電体層(104)を溶解させること、機械的に強化された洗浄を行うこと、または誘電体層(104)上に疎水性層(800)を化学吸着させることを含むことと、を含む。
【選択図】図2
Description
本出願は、2006年6月9日に出願された米国仮特許出願第60/804,425号の利益を主張するものである。
本発明は、概して、半導体システムに関するものであり、より具体的には、高度な半導体製造システムおよび半導体デバイスシステムに関するものである。
・酸化銅および強く結合した有機化合物をともなわない表面を確立するために、銅表面を洗浄するステップであって、この同じプロセスステップは、誘電体表面から汚染物質を除去する働きもする、ステップ、
・ウエハ表面から洗浄化学剤をすすぎ落とすステップ、
・銅特徴上に金属/金属合金キャップを選択的にデポジションするステップ、
・デポジションに起因するILD汚染を最小限に抑えるためなおかつ/もしくは膜の耐腐食性を助長するために、金属/金属合金キャップおよび/もしくはILDの後処理を行うステップ、
・ウエハ表面を脱イオン水ですすぐステップ、ならびに/またはウエハを乾燥させるステップ、
を含みうるいくつかのステップからなる。
a. キャッピング層のデポジション後における、
i. 不活性(N2など)環境内もしくは真空環境内におけるベーク、または
ii. 高温の不活性ガスを使用した乾燥
による熱処理。
上記の処理は、ともに、摂氏約30度から約150度までの温度で実施される。
b. 金属キャップ層のデポジション後に実施される、超臨界CO2を使用した臨界点乾燥(臨界点乾燥は、気体の密度と液体の密度とを等しく維持して気液界面を回避するために、亜臨界流体から超臨界流体までの溶液を使用する)。
c. 金属キャップ層のデポジション後に実施される、無水アルコールを非限定的な例として含む脱水剤を使用した乾燥。
d. ジ−t−ブチルジカーボネートおよび無水酢酸などを非限定的な例として含む水反応性の化学剤を使用した乾燥。これらの化合物と水との反応は、式1,2によって簡単に説明される。
(CH3)3COCOOCOOC(CH3)3 + H2O = 2CO2 + 2(CH3)3COH
無水酢酸については、
CH3COOCOCH3 + H2O = 2CH3COOH
これらの開始化学剤のさらなる利点は、それらの反応生成物が気体化合物または揮発性化合物のいずれかであることである。
このプロセスは、金属キャップ層デポジションプロセスの全手順の最終乾燥段階で実施される。より具体的には、金属/金属合金キャップデポジションプロセス後、ウエハは、概して、単純な化学的すすぎによって、または化学的すすぎをスクラブと組み合わせ、化学剤を含むもしくは含まない脱イオン水を使用して再びすすぐことによって、後洗浄され、ウエハは、次いで、非接着性の水を除去するためにスピン乾燥される。ウエハ上に水反応性の化学剤が導入されるのは、この段階の後である。水反応性の液体をウエハ表面全体に分布させた後、適切な反応時間を経た後に、ウエハはスピン乾燥され、プロセスは終了する。水反応性の液体の反応は、反応時間および反応収率を変更するために、室温または高温で実施することができる。
a. プロセスフローの乾燥ステップの後に導入されるプラズマ(例えばAr、N2、NH3、H2など)洗浄、
b. プロセス手順の最終ステップとしての超臨界CO2乾燥、
c. i. 錯化(ヒドロキシエチルエチレンジアミンテトラ酢酸(HEDTA)やシアン化物などの化学剤を使用した発熱プロセスにおいて結合を形成すること)もしくは
ii. ILD表面上の金属化合物の電荷およびILDの表面電荷を変化させること(すなわち、低pH溶液(pH<2)は、表面および金属化合物をともに正に帯電させ、後者は、金属イオンに結合した化合物をプロトン化して金属化合物/錯体を分解することによって実現される)
を通じて誘電体表面から金属イオンを除去すること、
d. ILD上に金属が形成されている場合にそれを低pH溶液に溶解させること、
e. ILDを溶解させて汚染物質を剥離させること、
f. 上記を組み合わせること、または
g. 上記の任意を機械的に強化された洗浄(例えばスクラブ)と組み合わせること、
によって表面汚染を除去するステップ。
パターン形成されたウエハが、表面から酸化銅を除去するために洗浄液に曝露され、次いで、すすがれ乾燥される。次いで、ウエハは、室温で300秒間にわたってトルエントリメトキシシランに曝露され、続いて、i−プロパノールおよび脱イオン水ですすがれる。これらのステップの後、ウエハは、さらなる洗浄ステップを経るか、あるいは無電解デポジションおよび必要に応じた後続の後洗浄を施されるかして、次いで、すすがれ乾燥される。このようにして得られた表面は、たとえ全デポジションプロセス後でも、強い疎水性を保持している。大抵の場合、表面の接触角は、未処理ウエハよりも、シラン処理のフルプロセス後のほうが大きくなる。シラン処理がない場合は、接触角は、未処理ウエハのそれより大幅に小さい。この主張は、酸化シリコン、またはBlack Diamondなどのその他の酸化シリコン含有誘電体材料についても有効である。
キャッピング層がデポジションされ、デポジション溶液を除去するためにウエハ表面がすすがれた後、ウエハは、表面から汚染物質を除去するためのスクラブを施される。スクラブ溶液は、腐食防止剤(すなわちトルオールトリアゾール、ベンゾトリアゾールなどのトリアゾール化合物)、脱酸素剤(すなわちL−アスコルビン酸)、および洗浄溶液のためのpH調整剤としても機能する錯化剤を含有している。このようなpH調整剤の1つは、シュウ酸である。この溶液のpHは、1.5から2.0までの間である。防止剤の濃度は、0.1〜10000ppmであり、最も好ましくは100〜2000ppmである。脱酸素剤の濃度は、0〜10000ppmであり、最も好ましくは1000〜5000ppmである。シュウ酸の濃度は、2〜50g/L、最も好ましくは5〜15g/Lである。
1. Cu構造上に金属キャップまたは金属合金キャップを形成した後に、
a. CuのCMPとキャッピング層のデポジションとの間における、
i. 不活性(N2、Arなど)環境内もしくは真空環境内におけるベーク、もしくは
ii. 高温の不活性ガスを使用した乾燥
による熱処理、
b. 超臨界CO2を使用した臨界点乾燥、
c. 無水アルコールを非限定的な例として含む脱水剤を使用した乾燥、または
d. 水反応性の化学剤を使用した乾燥、
などの様々な乾燥方法によって湿分を除去するステップ。
2. Cu構造上に金属キャップまたは金属合金キャップを形成した後に、
a. プラズマ(例えばAr、N2、NH3、H2など)洗浄、
b. 超臨界CO2表面乾燥、
c. i. 錯化(例えばHEDTA、シアン化物など)もしくは
ii. ILD表面上の金属化合物の電荷およびILDの表面電荷を変化させること
を通じて誘電体表面から金属イオンを除去すること、
d. 金属を低pH溶液に溶解させること、
e. ILDを溶解させて汚染物質を剥離させること、
f. 上記を組み合わせること、または
g. 上記の任意を機械的に強化された洗浄(例えばスクラブ)と組み合わせること、
によって表面汚染を除去するステップ。
3. Cu構造上に金属/金属合金キャップを形成する前(ILD上)または後(ILD、金属キャップ、もしくは両者)に、多官能基シラン(少なくとも1つの官能基が無極性であり、疎水性層形成プロセスの最中および後も原型をとどめる一方で、もう一方の1つもしくは複数の基は、基板と反応してシランを表面に結合させる)、または疎水性官能基とキャッピングプロセスの最中および後に表面上に保持されるのに十分な強さで表面に結合する少なくとも1つの無機酸基とからなる任意のハイブリッド化合物を使用して、疎水性層を形成することによって表面改質を行うステップ。
4. 疎水性層を形成する成分をデポジション溶液浴に含ませることによって表面改質を行うステップ。
Claims (26)
- 相互接続デバイスを作成する方法であって、
誘電体層(104)を提供し、
前記誘電体層(104)内に、前記誘電体層(104)の上部に露出される導体(108)を提供し、
前記露出された導体(108)をキャッピングし、
前記誘電体層(104)の表面の改質であって、前記導体(108)を低pH溶液に溶解させて前記誘電体層(104)から導体(108)イオンを洗浄し、前記導体(108)イオン下方の前記誘電体層(104)を溶解させ、機械的に強化された洗浄を行い、または前記誘電体層(104)上に疎水性層(800)を化学吸着させる
方法。 - 請求項1に記載の方法であって、
前記表面の改質は、キャッピング後に、不活性環境内もしくは真空環境内におけるベークまたは高温の不活性ガスによる熱処理を含む方法。 - 請求項1に記載の方法であって、
前記表面の改質は、キャッピング後における超臨界ガスによる臨界点乾燥を含む方法。 - 請求項1に記載の方法であって、
前記表面り改質は、キャッピング後における脱水剤、水反応性化学剤、またはそれらの組み合わせによる乾燥を含む方法。 - 請求項1に記載の方法であって、
前記表面の改質は、キャッピング後におけるプラズマ洗浄、超臨界ガス洗浄、またはそれらの組み合わせを含む方法。 - 請求項1に記載の方法であって、
前記表面の改質は、錯化によって前記誘電体層(104)から導体(108)イオンの洗浄を含む方法。 - 請求項1に記載の方法であって、
前記表面の改質は、前記導体(108)の電荷および前記誘電体層(104)の表面電荷を変化させることによって前記誘電体層(104)から導体(108)イオンの洗浄を含む方法。 - 相互接続デバイスを作成する方法であって、
誘電体層(104)を提供し、
前記誘電体層(104)内に、前記誘電体層(104)の上部に露出される導体(108)を提供し、
前記露出された導体(108)をキャッピングし、
前記誘電体層(104)の表面り改質であって、前記誘電体層(104)上、前記キャッピング層(400)(700)上、またはそれらの組み合わせ上に疎水性層(800)を形成する
方法。 - 請求項8に記載の方法であって、
前記表面の改質は、キャッピング後に、不活性環境内もしくは真空環境内におけるベークまたは高温の不活性ガスによる熱処理を含む方法。 - 請求項8に記載の方法であって、
前記表面の改質は、キャッピング後における超臨界ガスによる臨界点乾燥を含む方法。 - 請求項8に記載の方法であって、
前記表面の改質は、キャッピング後における脱水剤、水反応性化学剤、またはそれらの組み合わせによる乾燥を含む方法。 - 請求項8に記載の方法であって、
前記表面の改質は、キャッピング後におけるプラズマ洗浄、超臨界ガス洗浄、またはそれらの組み合わせを含む方法。 - 請求項8に記載の方法であって、
前記表面の改質は、錯化による前記誘電体層(104)からの導体(108)イオンの洗浄を含む方法。 - 請求項8に記載の方法であって、
前記表面の改質は、前記導体(108)の電荷および前記誘電体層(104)の表面電荷を変化させることによる前記誘電体層(104)からの導体(108)イオンの洗浄を含む方法。 - 相互接続デバイスを作成する方法であって、
誘電体層(104)を提供し、
前記誘電体層(104)内に、前記誘電体層(104)の上部に露出される導体(108)を提供し、
前記露出された導体(108)をキャップ材料でキャッピングし、
キャッピング直後における湿分除去、前記導体(108)またはキャップ材料の形成直後における表面汚染除去または疎水性層(800)形成、またはそれらの組み合わせによって、前記誘電体層(104)の表面を改質する
方法。 - 請求項15に記載の方法であって、
前記表面の改質は、キャッピング前に、摂氏約30度から約150度までの温度での、不活性環境内もしくは真空環境内におけるベークまたは高温の不活性ガスによる熱処理を含む方法。 - 請求項15に記載の方法であって、
前記表面の改質は、キャッピング後における二酸化炭素による臨界点乾燥を含む方法。 - 請求項15に記載の方法であって、
前記表面の改質は、キャッピング後における無水アルコール、水反応性ジ−t−ブチルジカーボネート、無水酢酸、またはそれらの組み合わせによる乾燥を含む方法。 - 請求項15に記載の方法であって、
前記表面の改質は、キャッピング後における非反応性ガスプラズマ洗浄、超臨界二酸化炭素洗浄、またはそれらの組み合わせを含む方法。 - 請求項15に記載の方法であって、
前記表面の改質は、HEDTAまたはシアン化物を使用した錯化によって前記誘電体層(104)から導体(108)イオンを洗浄することを含む方法。 - 請求項15に記載の方法であって、
前記表面の改質は、pHが2未満のpH溶液を使用して前記導体(108)の電荷および前記誘電体層(104)の表面電荷を変化させることによる前記誘電体層(104)からの導体(108)イオンの洗浄を含む方法。 - 請求項15に記載の方法であって、
前記表面の改質は、pHが2未満のpH溶液に前記導体(108)を溶解させて前記誘電体層(104)から導体(108)イオンを洗浄すること、前記導体(108)イオン下方の前記誘電体層(104)を溶解させて汚染物質を剥離させること、機械的なスクラブ洗浄を行うこと、またはそれらを組み合わせることを含む方法。 - 請求項15に記載の方法であって、
前記表面の改質は、非アミンシランまたは非チオールシランの疎水性層(800)の前記誘電体層(104)上への化学吸着を含む方法。 - 請求項15に記載の方法であって、
前記表面の改質は、前記誘電体層(104)上、前記キャッピング層(400)(700)上、またはそれらの組み合わせ上への、シラン、アザシラン、またはホスホン酸塩の疎水性層(800)の形成を含む方法。 - 請求項15に記載の方法であって、
前記表面の改質は、シラン蒸気、またはエチルアルコール、i−プロパノール、1−メチル−2−ピロリジノン、クロロホルム、ホスホン酸アルキル、もしくはリン酸アルキルを含む溶媒に対する曝露による前記誘電体層(104)上、前記キャッピング層(400)(700)上、またはそれらの組み合わせ上への疎水性層(800)の形成を含む方法。 - 請求項15に記載の方法であって、
前記表面の改質は、酸素の体積百分率が20%未満である大気中での、腐食防止剤または脱酸素剤を使用した前記ウエハの湿式洗浄を含む方法。
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