JP4077192B2 - Chemical mechanical polishing method and semiconductor device manufacturing method - Google Patents

Chemical mechanical polishing method and semiconductor device manufacturing method Download PDF

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JP4077192B2
JP4077192B2 JP2001367798A JP2001367798A JP4077192B2 JP 4077192 B2 JP4077192 B2 JP 4077192B2 JP 2001367798 A JP2001367798 A JP 2001367798A JP 2001367798 A JP2001367798 A JP 2001367798A JP 4077192 B2 JP4077192 B2 JP 4077192B2
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polishing
film
abrasive grains
chemical mechanical
semiconductor device
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JP2003168661A (en
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直明 桜井
俊秀 林
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Toshiba Corp
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Description

【０００１】
【発明の属する技術分野】
本発明は、半導体装置の製造工程に用いられる化学機械研磨（CMP; Chemical Mechanical Polishing）方法に関する。
【０００２】
【従来の技術】
例えば、半導体装置の動作速度の向上化等を目的としてＡｌ配線層に比べてより低抵抗であるＣｕ配線層を用いることが検討され、一部実用化されている。このＣｕ配線層は、表面の段差を解消する目的でＣＭＰ方法により形成されている。具体的には、半導体基板上の絶縁膜に配線形状の溝を形成し、前記溝を含む前記絶縁膜上にＣｕ膜を堆積し、前記Ｃｕ膜を研磨砥粒、酸化剤および水を含む研磨スラリーとポリシング装置とを用いてＣＭＰ処理し、前記溝内のみにＣｕ膜を残存させて埋め込み配線層を形成する。
【０００３】
ところで、Ｃｕ配線層の形成において研磨開始から研磨終了までの間に前記研磨砥粒、酸化剤および水を含み、かつ組成の異なる複数の研磨スラリーに切り替えて連続してＣＭＰ処理することが行われている。具体的には、Ｃｕ膜を半導体基板の絶縁膜に形成した溝に堆積するに先立って、埋込まれたＣｕ配線からのＣｕの拡散を防止する目的でＴａＮのような銅拡散防止膜を堆積した場合、Ｃｕの研磨途中で銅拡散防止膜が表面に露出するため、Ｃｕ膜の研磨スラリーと異なる組成の研磨スラリーに切り替えることが行われている。
【０００４】
しかしながら、前記連続的なＣＭＰにおいて始めに使用する研磨スラリーと次に使用する研磨スラリーをそれぞれ単体で研磨を行っても支障がない場合でも、連続して研磨すると後続の研磨スラリー中の研磨砥粒が凝集して研磨面（例えばＣｕ膜表面）にスクラッチが生じる虞があった。
【０００５】
【発明が解決しようとする課題】
本発明は、連続的な研磨途中で組成の異なる研磨スラリーに切り替えてもその中の研磨砥粒の凝集を防止することが可能な化学機械研磨方法を提供するものである。
【０００６】
【課題を解決するための手段】
本発明に係る化学機械研磨方法は、基板上の各種被膜を研磨開始から研磨終了までの間に研磨砥粒、酸化剤、界面活性剤および水を含み、かつ組成の異なる複数の研磨スラリーに切り替えて連続して化学機械研磨する方法であって、
前記各研磨スラリーは、前記各界面活性剤が同じイオン性を持ち、それらの中の研磨砥粒は互いに材料が異なると共に、各研磨砥粒が示すゼータ電位の極性が同一であることを特徴とするものである。
本発明に係る半導体装置の製造方法は、半導体基板上に各種被膜を形成する工程と、
前記各種被膜を研磨開始から研磨終了までの間に、研磨砥粒、酸化剤、界面活性剤および水を含み、かつ組成の異なる複数の研磨スラリーに切り替えて、連続して化学機械研磨を行う工程とを有し、
前記各研磨スラリーは、前記各界面活性剤が同じイオン性を持ち、それらの中の研磨砥粒は互いに材料が異なると共に、各研磨砥粒が示すゼータ電位の極性が同一であることを特徴とするものである。
【０００７】
【発明の実施の形態】
以下、本発明に係る化学機械研磨方法を詳細に説明する。
【０００８】
この化学機械研磨方法は、基板上の各種被膜を研磨開始から研磨終了までの間に研磨砥粒、酸化剤および水を含み、かつ組成の異なる複数の研磨スラリーに切り替えて連続して化学機械研磨するに際し、前記各研磨スラリーとしてそれらの中の研磨砥粒がスラリー中で示すゼータ電位の極性を同一にしたものを用いる。
【０００９】
前記基板上の各種被膜としては、例えばＣｕ膜、Ｃｕ合金膜、またはＴａＮ、ＴａＮｂ、Ｗ，ＷＮ，ＴａＮ，ＴａＳｉＮ，Ｔａ，Ｃｏ，Ｚｒ，ＺｒＮおよびＣｕＴａ合金から選ばれる１層または２層以上の銅拡散防止膜等を挙げることができる。
【００１０】
前記研磨スラリー中の研磨砥粒としては、例えばシリカ（コロイダルシリカを含む）、アルミナ（コロイダルアルミナを含む）、酸化セリウム等を挙げることができる。
【００１１】
前記各研磨スラリー中の前記酸化剤としては、例えば過酸化水素（Ｈ2 Ｏ2 ）、次亜塩素酸ソーダ（ＮａＣｌＯ）等を用いることができる。
【００１２】
前記各研磨スラリー中には、さらに両性イオン性、陰イオン性、陽イオン性の界面活性剤が添加されることを許容する。このような界面活性剤の使用においては、同じイオン性を持つものが選ばれる。前記両性イオン性界面活性剤としては、例えばイミダゾリベタイン等を挙げることができる。前記陰イオン性界面活性剤としては、例えばドデシル硫酸ナトリウム、ドデシル硫酸アンモニウム等を挙げることができる。前記陽イオン性界面活性剤としては、例えばステアリントリメチルアンモニウムクロライド等を挙げることができる。
【００１３】
前記各研磨スラリー中には、さらにキレート剤が添加されることを許容する。このキレート剤としては、各種の有機酸を用いることができるが、特に各種被膜としてＣｕ膜またはＣｕ合金膜を用いる場合には２−キノリンカルボン酸（キナルジン酸）、２−ピリジンカルボン酸、２，６−ピリジンカルボン酸、キノン等が好ましい。
【００１４】
前記各研磨スラリー中には、さらに乳酸等のｐＨ調整剤が添加されることを許容する。
【００１５】
前述したＣＭＰにあたっては、例えば図１に示すポリシング装置が用いられる。すなわち、ターンテーブル１上には例えば布、独立気泡を有するポリウレタン発泡体から作られた研磨パッド２が被覆されている。研磨スラリーを供給するための供給管３は、前記研磨パッド２の上方に配置されている。上面に支持軸４を有する基板ホルダ５は、研磨パッド２の上方に上下動自在でかつ回転自在に配置されている。
【００１６】
このようなポリシング装置において、前記ホルダ５により基板６をその研磨面（被膜）が前記研磨パッド２に対向するように保持し、前記供給管３から前述した組成の研摩スラリー７を供給しながら、前記支持軸４により前記基板６を前記研磨パッド２に向けて所望の加重を与え、さらに前記ホルダ５および前記ターンテーブル１をそれぞれ同方向に回転させることにより前記基板６上の被膜が研磨される。
【００１７】
本発明に係る化学機械研磨方法は、次のような半導体装置の製造方法に適用することができる。
【００１８】
まず、半導体基板上の絶縁膜に配線層の形状に相当する溝およびビアフィルの形状に相当する開口部から選ばれる少なくとも１つの埋込み用部材を形成する。この埋込み用部材の内面を含む前記絶縁膜上に銅拡散防止膜を形成する。この銅拡散防止膜上に銅または銅合金からなる配線材料膜を形成する。研磨砥粒と酸化剤と水とを含有する第１研磨組成物を用いて前記配線材料膜を研磨する。この研磨過程で前記銅拡散防止膜が露出する直前もしくは直後に表面が前記第１研磨組成物により濡れた状態で研磨砥粒と酸化剤と水とを含有する第２研磨組成物に切り替えて前記銅拡散防止膜を研磨して前記埋込み部材内に前記銅拡散防止膜で覆われた状態で埋込まれた配線層（またはビアフィル）を形成する。このような配線層等の形成において、第２研磨スラリーとしてその研磨砥粒が示すゼータ電位と前記第１研磨スラリー中で研磨砥粒が示すゼータ電位とが同一極性で、かつ前記第１研磨組成物中の酸化剤より多い量の酸化剤を含む組成のものを用いる。
【００１９】
前記銅拡散防止膜としては、例えばＴａＮ、ＴａＮｂ、Ｗ，ＷＮ，ＴａＮ，ＴａＳｉＮ，Ｔａ，Ｃｏ，Ｚｒ，ＺｒＮおよびＣｕＴａ合金から選ばれる１層または２層以上のものを挙げることができる。
【００２０】
前記第１，第２の研磨スラリー中の研磨砥粒、酸化剤は、前述したのと同様なものを用いることができる。
【００２１】
前記第１，第２の研磨スラリー中には、さらに前述した両性イオン性、陰イオン性、陽イオン性の界面活性剤、キレート剤、ｐＨ調整剤が添加されることを許容する。
【００２２】
前記第１研磨スラリーは、ＣｕまたはＣｕ合金の配線材料膜に対した高い研磨性を示し、前記第２研磨スラリーは配線材料膜と銅拡散防止膜の両者を略同じ速度で研磨する性質を有する。
【００２３】
前記配線材料膜、配線材料膜と銅拡散防止膜の研磨にあたっては、前述したポリシング装置が用いられる。
【００２４】
以上説明した本発明に係る化学機械研磨方法は、基板上の各種被膜を研磨開始から研磨終了までの間に研磨砥粒、酸化剤および水を含み、かつ組成の異なる複数の研磨スラリーに切り替えて連続して化学機械研磨するに際し、前記各研磨スラリーとしてそれらの中の研磨砥粒がスラリー中で示すゼータ電位の極性を同一にしたものを用いる。
【００２５】
このような方法によれば、研磨開始から研磨終了までの間に複数の研磨スラリーに切り替えて連続的に研磨するに際し、研磨砥粒がスラリー中で示すゼータ電位の極性を同一にした研磨スラリーを用いることによって、初期研磨後の第２研磨以降において研磨スラリー中の研磨砥粒の凝集を防止できるため、基板上の各種被膜にスクラッチが発生するのを防止できる。
【００２６】
【実施例】
以下、好ましい実施例を詳細に説明する。
【００２７】
下記表１に示す組成、ｐＨおよびゼータ電位（研磨砥粒がスラリー中で示すゼータ電位）を有する４種の研磨スラリーＡ〜研磨スラリーＤを調製した。
【００２８】
【表１】

Figure 0004077192
【００２９】
（実施例１）
まず、表面に厚さ１０００ｎｍのＣｕ膜を成膜した８インチシリコンウェハ（シリコン基板）を用意した。
【００３０】
次いで、前述した図１に示すポリシング装置のホルダ５により前記基板６をそのＣｕ膜が研磨パッド２に対向するように保持し、供給管３から前記表１の研磨スラリーＡを２００ｃｃ／分を供給しながら、支持軸４により前記基板６を前記研磨パッド２に向けて２００ｇ／ｃｍ2の荷重を与え、さらに前記ホルダ５および前記ターンテーブル１をそれぞれ６０ｒｐｍ，６３ｒｐｍの速度で同方向に回転させることにより前記基板６上Ｃｕ膜を３０秒間研磨した（第１研磨）。つづいて、供給管３から前記研磨スラリーＡの供給を停止し、供給管３から前記表１に示す研磨スラリーＣを研磨スラリーＡが付着された研磨パッド２に供給しながら、同様な条件で前記基板６のＣｕ膜を３０秒間研磨した（第２研磨）。その後、純水ブラシで１分間洗浄した後に２０００ｒｐｍの条件でスピン乾燥を行った。
【００３１】
（実施例２）
第１研磨を前記表１に示す研磨スラリーＢ、第２研磨を前記表１に示す研磨スラリーＤを用いて行った以外、実施例１と同様な条件で基板表面のＣｕ膜を連続して研磨し、洗浄、乾燥した。
【００３２】
（比較例１）
第１研磨を前記表１に示す研磨スラリーＡ、第２研磨を前記表１に示す研磨スラリーＢを用いて行った以外、実施例１と同様な条件で基板表面のＣｕ膜を連続して研磨し、洗浄、乾燥した。
【００３３】
（比較例２）
第１研磨を前記表１に示す研磨スラリーＡ、第２研磨を前記表１に示す研磨スラリーＤを用いて行った以外、実施例１と同様な条件で基板表面のＣｕ膜を連続して研磨し、洗浄、乾燥した。
【００３４】
実施例１，２および比較例１，２の連続研磨後にＣｕ膜表面の１μｍ以上のスクラッチを検査装置（KLA-Tencor社製商品名;SFS6420）と電子顕微鏡を用いて調べた。その結果を下記表２に示す。
【００３５】
【表２】
Figure 0004077192
【００３６】
前記表２から明らかなように第１，第２のＣｕ研磨においてゼータ電位の極性が異なる研磨スラリーを用いる比較例１，２では連続研磨後のＣｕ膜表面のスクラッチ数が３５，１８と多くなることがわかる。これに対し、第１，第２のＣｕ研磨においてゼータ電位の極性が同じ研磨スラリーを用いる実施例１，２では連続研磨後のＣｕ膜表面のスクラッチ数が１以下と優れた研磨特性を示すことがわかる。
【００３７】
（実施例３）
まず、図２の（Ａ）に示すように表面に図示しないソース、ドレイン等の拡散層が形成されたシリコン基板１１上にＣＶＤ法により層間絶縁膜としての例えば厚さ１０００ｎｍのＳｉＯ2 膜１２を堆積した後、前記ＳｉＯ2 膜１２にフォトエッチング技術により配線層に相当する形状を有する深さ５００ｎｍの複数の溝１３を形成した。つづいて、図２の（Ｂ）に示すように前記溝１３を含む前記ＳｉＯ2 膜１２上にスパッタ蒸着により厚さ１５ｎｍのＴａＮからなる銅拡散防止膜１４および厚さ６００ｎｍのＣｕ膜１５をこの順序で形成した。
【００３８】
次いで、前述した図１に示すポリシング装置の基板ホルダ５に図２の（Ｂ）に示す基板１１を逆さにして保持し、前記ホルダ５の支持軸４により前記基板をターンテーブル１上のローデル社製商品名；ＩＣ１０００からなる研磨パッド２に５００ｇ／ｃｍ2 の荷重を与え、前記ターンテーブル１およびホルダ５をそれぞれ１０３ｒｐｍ、１００ｒｐｍの速度で同方向に回転させながら、第１研磨スラリーを供給管３から５０ｍｌ／分の速度で前記研磨パッド２に供給して前記基板１１に形成したＣｕ膜１５を前記ＳｉＯ2 膜１２上の前記銅拡散防止膜１４の表面が露出するまで研磨した。ここで、前記第１研磨スラリーとして２−キノリンカルボン酸（キナルジン酸）０．５７重量％、過酸化水素３．７８重量％、アルミナ１．０９重量％、乳酸０．６７重量％、ドデシル硫酸アンモニウム１．００重量％および水の組成（ｐＨ；３、ゼータ電位；−２０ｍＶ）を有するものを用いた。
【００３９】
次いで、前記供給管３から前記第１研磨スラリーの供給を停止し、供給管３から下記組成の第２研磨スラリーを第１研磨スラリーが付着された研磨パッド２に供給しながら、同様な条件で前記基板１１の銅拡散防止膜およびＣｕ膜を連続的に研磨した。ここで前記第２研磨スラリーとして２−キノリンカルボン酸０．５７重量％、過酸化水素４．６７重量％、コロイダルシリカ５．０重量％、乳酸０．６７重量％、ドデシル硫酸アンモニウム１．００重量％および水の組成（ｐＨ；３、ゼータ電位；−２５ｍＶ）を有するものを用いた。このような第２研磨スラリーによる研磨によって、図２の（Ｃ）に示すように前記溝１３内に銅拡散防止膜１４が残存すると共に、前記銅拡散防止膜１４で覆われた前記溝１３内に前記ＳｉＯ2 膜１２表面とほぼ面一な埋め込みＣｕ配線層１６が形成された。
【００４０】
また、前記Ｃｕ配線層１６表面を検査装置（KLA-Tencor社製商品名;SFS6420）と電子顕微鏡を用いて調べたところ、前記Ｃｕ配線層１６表面へのスクラッチの発生は殆ど認められなかった。
【００４１】
【発明の効果】
以上詳述したように本発明によれば、連続的な研磨途中で組成の異なる研磨スラリーに切り替えてもその中の研磨砥粒の凝集を防止して研磨表面へのスクラッチの発生を防止することが可能な化学機械研磨方法を提供することができる。
【図面の簡単な説明】
【図１】本発明の研磨工程に使用されるポリシング装置を示す概略図。
【図２】本発明の実施例３における半導体装置の製造工程を示す断面図。
【符号の説明】
１…ターンテーブル、
２…研磨パッド、
３…供給管、
５…ホルダ、
１１，…シリコン基板、
１３…溝、
１４…銅拡散防止膜、
１５…Ｃｕ膜、
１６…Ｃｕ配線層。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a chemical mechanical polishing (CMP) method used in a semiconductor device manufacturing process.
[0002]
[Prior art]
For example, the use of a Cu wiring layer having a lower resistance than that of an Al wiring layer for the purpose of improving the operation speed of a semiconductor device has been studied and partly put into practical use. This Cu wiring layer is formed by the CMP method for the purpose of eliminating the surface level difference. Specifically, a wiring-shaped groove is formed in an insulating film on a semiconductor substrate, a Cu film is deposited on the insulating film including the groove, and the Cu film is polished including polishing abrasives, an oxidizing agent, and water. A CMP process is performed using a slurry and a polishing apparatus, and a Cu film is left only in the groove to form a buried wiring layer.
[0003]
By the way, in the formation of the Cu wiring layer, CMP processing is continuously performed by switching to a plurality of polishing slurries containing the abrasive grains, the oxidant, and water and having different compositions between the start of polishing and the end of polishing. ing. Specifically, prior to depositing the Cu film in the groove formed in the insulating film of the semiconductor substrate, a copper diffusion prevention film such as TaN is deposited for the purpose of preventing Cu diffusion from the embedded Cu wiring. In this case, since the copper diffusion preventing film is exposed on the surface during the polishing of Cu, switching to a polishing slurry having a composition different from that of the polishing slurry for the Cu film is performed.
[0004]
However, even if the polishing slurry used first in the continuous CMP and the polishing slurry used next are not hindered by single polishing, the polishing abrasive grains in the subsequent polishing slurry can be polished continuously. May aggregate and scratches may occur on the polished surface (for example, Cu film surface).
[0005]
[Problems to be solved by the invention]
The present invention provides a chemical mechanical polishing method capable of preventing agglomeration of abrasive grains therein even when switching to a polishing slurry having a different composition during continuous polishing.
[0006]
[Means for Solving the Problems]
In the chemical mechanical polishing method according to the present invention, various coatings on a substrate are switched to a plurality of polishing slurries containing abrasive grains, an oxidizing agent, a surfactant and water and having different compositions between the start of polishing and the end of polishing. A continuous chemical mechanical polishing method,
In each of the polishing slurries, the surfactants have the same ionicity, and the abrasive grains in them have different materials , and the polarity of the zeta potential exhibited by the abrasive grains is the same. To do.
A method of manufacturing a semiconductor device according to the present invention includes a step of forming various films on a semiconductor substrate,
A process of performing chemical mechanical polishing continuously by switching to a plurality of polishing slurries containing polishing abrasive grains, an oxidizing agent, a surfactant and water and having different compositions between the start of polishing and the end of polishing of the various coating films. And
In each of the polishing slurries, the surfactants have the same ionicity, and the abrasive grains in them have different materials , and the polarity of the zeta potential exhibited by the abrasive grains is the same. To do.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the chemical mechanical polishing method according to the present invention will be described in detail.
[0008]
In this chemical mechanical polishing method, chemical mechanical polishing is continuously performed by switching to a plurality of polishing slurries containing abrasive grains, an oxidizing agent and water and having different compositions between the start of polishing and the end of polishing of various coatings on the substrate. In this case, the polishing slurry having the same zeta potential polarity as the polishing abrasive grains in the slurry is used as each of the polishing slurries.
[0009]
The various coatings on the substrate include, for example, a Cu film, a Cu alloy film, or one or more layers selected from TaN, TaNb, W, WN, TaN, TaSiN, Ta, Co, Zr, ZrN, and CuTa alloy. Examples thereof include a copper diffusion prevention film.
[0010]
Examples of the abrasive grains in the polishing slurry include silica (including colloidal silica), alumina (including colloidal alumina), cerium oxide, and the like.
[0011]
As the oxidizing agent in each polishing slurry, for example, hydrogen peroxide (H 2 O 2 ), sodium hypochlorite (NaClO), or the like can be used.
[0012]
A zwitterionic, anionic, or cationic surfactant is allowed to be further added to each of the polishing slurries. In the use of such a surfactant, those having the same ionicity are selected. Examples of the zwitterionic surfactant include imidazolibetaine. Examples of the anionic surfactant include sodium dodecyl sulfate and ammonium dodecyl sulfate. Examples of the cationic surfactant include stearic trimethyl ammonium chloride.
[0013]
A chelating agent is allowed to be further added to each of the polishing slurries. As this chelating agent, various organic acids can be used. Particularly when a Cu film or a Cu alloy film is used as various coatings, 2-quinolinecarboxylic acid (quinaldic acid), 2-pyridinecarboxylic acid, 2, 6-pyridinecarboxylic acid, quinone and the like are preferable.
[0014]
It is allowed that a pH adjuster such as lactic acid is further added to each of the polishing slurries.
[0015]
In the above-described CMP, for example, a polishing apparatus shown in FIG. 1 is used. That is, the turntable 1 is covered with a polishing pad 2 made of, for example, a cloth or a polyurethane foam having closed cells. A supply pipe 3 for supplying polishing slurry is disposed above the polishing pad 2. A substrate holder 5 having a support shaft 4 on its upper surface is disposed above the polishing pad 2 so as to be vertically movable and rotatable.
[0016]
In such a polishing apparatus, the holder 5 holds the substrate 6 so that the polishing surface (coating film) faces the polishing pad 2, and while supplying the polishing slurry 7 having the above-described composition from the supply pipe 3, The support shaft 4 applies a desired load to the substrate 6 toward the polishing pad 2, and the coating on the substrate 6 is polished by rotating the holder 5 and the turntable 1 in the same direction. .
[0017]
The chemical mechanical polishing method according to the present invention can be applied to the following semiconductor device manufacturing method.
[0018]
First, at least one embedding member selected from a groove corresponding to the shape of the wiring layer and an opening corresponding to the shape of the via fill is formed in the insulating film on the semiconductor substrate. A copper diffusion preventing film is formed on the insulating film including the inner surface of the embedding member. A wiring material film made of copper or a copper alloy is formed on the copper diffusion preventing film. The wiring material film is polished using a first polishing composition containing abrasive grains, an oxidizing agent, and water. In this polishing process, the surface is wetted with the first polishing composition immediately before or after the copper diffusion prevention film is exposed, and the second polishing composition containing abrasive grains, oxidant, and water is switched to the second polishing composition. The copper diffusion prevention film is polished to form a wiring layer (or via fill) embedded in the embedded member while being covered with the copper diffusion prevention film. In the formation of such a wiring layer or the like, the zeta potential indicated by the abrasive grains as the second polishing slurry and the zeta potential indicated by the abrasive grains in the first polishing slurry have the same polarity, and the first polishing composition A composition having a larger amount of oxidizing agent than the oxidizing agent in the product is used.
[0019]
Examples of the copper diffusion preventing film include one or more layers selected from TaN, TaNb, W, WN, TaN, TaSiN, Ta, Co, Zr, ZrN, and CuTa alloy.
[0020]
As the abrasive grains and the oxidizing agent in the first and second polishing slurries, the same ones as described above can be used.
[0021]
In the first and second polishing slurries, the above-described zwitterionic, anionic, and cationic surfactants, chelating agents, and pH adjusting agents are allowed to be added.
[0022]
The first polishing slurry exhibits high polishability for a Cu or Cu alloy wiring material film, and the second polishing slurry has a property of polishing both the wiring material film and the copper diffusion prevention film at substantially the same speed. .
[0023]
In polishing the wiring material film, the wiring material film, and the copper diffusion prevention film, the above-described polishing apparatus is used.
[0024]
In the chemical mechanical polishing method according to the present invention described above, various coatings on the substrate are switched to a plurality of polishing slurries containing polishing abrasive grains, an oxidizing agent and water and having different compositions between the start of polishing and the end of polishing. When performing continuous chemical mechanical polishing, the polishing slurry having the same zeta potential polarity shown in the slurry is used as each of the polishing slurries.
[0025]
According to such a method, when switching to a plurality of polishing slurries and continuously polishing between the start of polishing and the end of polishing, a polishing slurry in which the polarity of the zeta potential indicated by the abrasive grains in the slurry is the same. By using it, it is possible to prevent agglomeration of abrasive grains in the polishing slurry after the second polishing after the initial polishing, and thus it is possible to prevent the occurrence of scratches on various coatings on the substrate.
[0026]
【Example】
Hereinafter, preferred embodiments will be described in detail.
[0027]
Four types of polishing slurries A to D having the composition, pH, and zeta potential (the zeta potential that the abrasive grains show in the slurry) shown in Table 1 below were prepared.
[0028]
[Table 1]
Figure 0004077192
[0029]
Example 1
First, an 8-inch silicon wafer (silicon substrate) having a Cu film having a thickness of 1000 nm formed on the surface was prepared.
[0030]
Next, the substrate 6 is held by the above-mentioned polishing apparatus holder 5 shown in FIG. 1 so that the Cu film faces the polishing pad 2, and 200 cc / min of the polishing slurry A shown in Table 1 is supplied from the supply pipe 3. While, a load of 200 g / cm 2 is applied to the polishing pad 2 by the support shaft 4 and the holder 5 and the turntable 1 are rotated in the same direction at a speed of 60 rpm and 63 rpm, respectively. Then, the Cu film on the substrate 6 was polished for 30 seconds (first polishing). Subsequently, the supply of the polishing slurry A from the supply pipe 3 is stopped, and the polishing slurry C shown in Table 1 is supplied from the supply pipe 3 to the polishing pad 2 to which the polishing slurry A is adhered. The Cu film on the substrate 6 was polished for 30 seconds (second polishing). Thereafter, after washing with a pure water brush for 1 minute, spin drying was performed under the condition of 2000 rpm.
[0031]
(Example 2)
The Cu film on the substrate surface is continuously polished under the same conditions as in Example 1 except that the first polishing is performed using the polishing slurry B shown in Table 1 and the second polishing is performed using the polishing slurry D shown in Table 1. And washed and dried.
[0032]
(Comparative Example 1)
The Cu film on the substrate surface is continuously polished under the same conditions as in Example 1 except that the first polishing is performed using the polishing slurry A shown in Table 1 and the second polishing is performed using the polishing slurry B shown in Table 1. And washed and dried.
[0033]
(Comparative Example 2)
The Cu film on the substrate surface is continuously polished under the same conditions as in Example 1 except that the first polishing is performed using the polishing slurry A shown in Table 1 and the second polishing is performed using the polishing slurry D shown in Table 1. And washed and dried.
[0034]
After continuous polishing of Examples 1 and 2 and Comparative Examples 1 and 2, scratches of 1 μm or more on the surface of the Cu film were examined using an inspection apparatus (trade name, manufactured by KLA-Tencor; SFS6420) and an electron microscope. The results are shown in Table 2 below.
[0035]
[Table 2]
Figure 0004077192
[0036]
As apparent from Table 2, in Comparative Examples 1 and 2 using polishing slurries having different zeta potential polarities in the first and second Cu polishings, the number of scratches on the Cu film surface after continuous polishing increases to 35 and 18. I understand that. On the other hand, in Examples 1 and 2 using the polishing slurry having the same zeta potential polarity in the first and second Cu polishing, the number of scratches on the surface of the Cu film after continuous polishing is 1 or less and shows excellent polishing characteristics. I understand.
[0037]
(Example 3)
First, as shown in FIG. 2A, a SiO 2 film 12 having a thickness of, for example, 1000 nm as an interlayer insulating film is formed by CVD on a silicon substrate 11 on which diffusion layers such as source and drain (not shown) are formed on the surface. After the deposition, a plurality of grooves 13 having a depth of 500 nm having a shape corresponding to the wiring layer was formed in the SiO 2 film 12 by a photoetching technique. Subsequently, as shown in FIG. 2B, a copper diffusion prevention film 14 made of TaN having a thickness of 15 nm and a Cu film 15 having a thickness of 600 nm are formed on the SiO 2 film 12 including the groove 13 by sputtering deposition. Formed in order.
[0038]
Next, the substrate 11 shown in FIG. 2B is held upside down on the substrate holder 5 of the polishing apparatus shown in FIG. 1 described above, and the substrate is held by the Rodel company on the turntable 1 by the support shaft 4 of the holder 5. Product name: A load of 500 g / cm 2 is applied to the polishing pad 2 made of IC1000, and the first polishing slurry is supplied to the supply pipe 3 while rotating the turntable 1 and the holder 5 in the same direction at a speed of 103 rpm and 100 rpm, respectively. Then, the Cu film 15 supplied to the polishing pad 2 at a rate of 50 ml / min and formed on the substrate 11 was polished until the surface of the copper diffusion preventing film 14 on the SiO 2 film 12 was exposed. Here, as the first polishing slurry, 0.57% by weight of 2-quinolinecarboxylic acid (quinaldic acid), 3.78% by weight of hydrogen peroxide, 1.09% by weight of alumina, 0.67% by weight of lactic acid, ammonium dodecyl sulfate 1 Those having 0.000% by weight and water composition (pH: 3, zeta potential: -20 mV) were used.
[0039]
Next, the supply of the first polishing slurry from the supply pipe 3 is stopped, and the second polishing slurry having the following composition is supplied from the supply pipe 3 to the polishing pad 2 to which the first polishing slurry is attached, under the same conditions. The copper diffusion preventing film and the Cu film on the substrate 11 were continuously polished. Here, as the second polishing slurry, 0.57% by weight of 2-quinolinecarboxylic acid, 4.67% by weight of hydrogen peroxide, 5.0% by weight of colloidal silica, 0.67% by weight of lactic acid, and 1.00% by weight of ammonium dodecyl sulfate. And those having a water composition (pH; 3, zeta potential: -25 mV). By such polishing with the second polishing slurry, the copper diffusion prevention film 14 remains in the groove 13 as shown in FIG. 2C, and the groove 13 covered with the copper diffusion prevention film 14 Then, a buried Cu wiring layer 16 substantially flush with the surface of the SiO 2 film 12 was formed.
[0040]
Further, when the surface of the Cu wiring layer 16 was examined using an inspection device (trade name, manufactured by KLA-Tencor; SFS6420) and an electron microscope, almost no scratches were observed on the surface of the Cu wiring layer 16.
[0041]
【The invention's effect】
As described above in detail, according to the present invention, even when switching to a polishing slurry having a different composition during continuous polishing, it prevents agglomeration of abrasive grains therein and prevents generation of scratches on the polishing surface. It is possible to provide a chemical mechanical polishing method capable of
[Brief description of the drawings]
FIG. 1 is a schematic view showing a polishing apparatus used in a polishing process of the present invention.
FIG. 2 is a cross-sectional view showing a manufacturing process of a semiconductor device in Example 3 of the present invention.
[Explanation of symbols]
1 ... Turntable,
2 ... polishing pad,
3 ... supply pipe,
5 ... Holder,
11, ... silicon substrate,
13 ... Groove,
14 ... Copper diffusion prevention film,
15 ... Cu film,
16: Cu wiring layer.

Claims (8)

基板上の各種被膜を研磨開始から研磨終了までの間に研磨砥粒、酸化剤、界面活性剤および水を含み、かつ組成の異なる複数の研磨スラリーに切り替えて連続して化学機械研磨する方法であって、
前記各研磨スラリーは、前記各界面活性剤が同じイオン性を持ち、それらの中の研磨砥粒は互いに材料が異なると共に、各研磨砥粒が示すゼータ電位の極性が同一であることを特徴とする化学機械研磨方法。A method of continuously chemically and mechanically polishing various coatings on a substrate by switching to a plurality of polishing slurries containing polishing abrasive grains, an oxidant, a surfactant, and water between the start of polishing and the end of polishing. There,
In each of the polishing slurries, the surfactants have the same ionicity, and the abrasive grains in them have different materials , and the polarity of the zeta potential exhibited by the abrasive grains is the same. Chemical mechanical polishing method. 前記各研磨スラリーは、さらにキレート剤を含有することを特徴とする請求項１記載の化学機械研磨方法。  2. The chemical mechanical polishing method according to claim 1, wherein each of the polishing slurries further contains a chelating agent. 前記各研磨スラリーは、さらにｐＨ調整剤を含有することを特徴とする請求項１または２記載の化学機械研磨方法。 3. The chemical mechanical polishing method according to claim 1, wherein each of the polishing slurries further contains a pH adjusting agent. 前記各種被膜のいずれか一つは、Ｃｕを有する膜であることを特徴とする請求項１ないし３いずれか記載の化学機械研磨方法。Any one of the various coatings, claims 1 to 3 chemical mechanical polishing method of any characterized in that it is a film having a Cu. 半導体基板上に各種被膜を形成する工程と、
前記各種被膜を研磨開始から研磨終了までの間に、研磨砥粒、酸化剤、界面活性剤および水を含み、かつ組成の異なる複数の研磨スラリーに切り替えて、連続して化学機械研磨を行う工程とを有し、
前記各研磨スラリーは、前記各界面活性剤が同じイオン性を持ち、それらの中の研磨砥粒は互いに材料が異なると共に、各研磨砥粒が示すゼータ電位の極性が同一であることを特徴とする半導体装置の製造方法。Forming various coatings on the semiconductor substrate;
A process of performing chemical mechanical polishing continuously by switching to a plurality of polishing slurries containing polishing abrasive grains, an oxidizing agent, a surfactant and water and having different compositions between the start of polishing and the end of polishing of the various coating films. And
In each of the polishing slurries, the surfactants have the same ionicity, and the abrasive grains in them have different materials , and the polarity of the zeta potential exhibited by the abrasive grains is the same. A method for manufacturing a semiconductor device. 前記各研磨スラリーは、さらにキレート剤を含有することを特徴とする請求項５記載の半導体装置の製造方法。6. The method of manufacturing a semiconductor device according to claim 5 , wherein each of the polishing slurries further contains a chelating agent. 前記各研磨スラリーは、さらにｐＨ調整剤を含有することを特徴とする請求項５または６記載の半導体装置の製造方法。7. The method of manufacturing a semiconductor device according to claim 5 , wherein each of the polishing slurries further contains a pH adjuster. 前記各種被膜は、Ｃｕを有する膜および銅拡散膜であることを特徴とする請求項５ないし７いずれか記載の半導体装置の製造方法。The various coatings, the method of manufacturing a semiconductor device according to any one of claims 5 to 7, characterized in that a film and copper diffusion film having a Cu.
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