JP4951808B2 - Polishing liquid for metal and polishing method - Google Patents
Polishing liquid for metal and polishing method Download PDFInfo
- Publication number
- JP4951808B2 JP4951808B2 JP2000327296A JP2000327296A JP4951808B2 JP 4951808 B2 JP4951808 B2 JP 4951808B2 JP 2000327296 A JP2000327296 A JP 2000327296A JP 2000327296 A JP2000327296 A JP 2000327296A JP 4951808 B2 JP4951808 B2 JP 4951808B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- polishing
- acid
- polishing liquid
- pyrimidine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 238000005498 polishing Methods 0.000 title claims description 159
- 229910052751 metal Inorganic materials 0.000 title claims description 122
- 239000002184 metal Substances 0.000 title claims description 122
- 239000007788 liquid Substances 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 28
- 239000000758 substrate Substances 0.000 claims description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 27
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 23
- 230000004888 barrier function Effects 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920003169 water-soluble polymer Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- -1 tungsten nitride Chemical class 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 9
- 239000012964 benzotriazole Substances 0.000 claims description 9
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 7
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 7
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- 150000003852 triazoles Chemical group 0.000 claims description 5
- LHCPRYRLDOSKHK-UHFFFAOYSA-N 7-deaza-8-aza-adenine Chemical group NC1=NC=NC2=C1C=NN2 LHCPRYRLDOSKHK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 3
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Weting (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、特に半導体デバイスの配線工程において好適に用いられる金属用研磨液及びそれを用いた研磨法に関する。
【０００２】
【従来の技術】
近年、半導体集積回路（ＬＳＩ）の高集積化、高性能化に伴って新たな微細加工技術が開発されている。化学機械研磨（ＣＭＰ）法もその一つであり、ＬＳＩ製造工程、特に多層配線形成工程における層間絶縁膜の平坦化、金属プラグ形成、埋め込み配線形成において頻繁に利用される技術である。この技術は、例えば米国特許第４９４４８３６号明細書に開示されている。
【０００３】
近年、ＬＳＩを高性能化するために、配線材料として銅合金の利用が試みられている。しかし、銅合金は従来のアルミニウム合金配線の形成で頻繁に用いられたドライエッチング法による微細加工が困難である。そこで、あらかじめ溝を形成してある絶縁膜上に銅合金薄膜を堆積して埋め込み、溝部以外の銅合金薄膜をＣＭＰにより除去して埋め込み配線を形成する、いわゆるダマシン法が主に採用されている。この技術は、例えば特開平２−２７８８２２号公報に開示されている。
【０００４】
金属のＣＭＰの一般的な方法は、円形の研磨定盤（プラテン）上に研磨パッドを貼り付け、研磨パッド表面を金属用研磨液で浸し、基体の金属膜を形成した面を押し付けて、その裏面から所定の圧力（研磨圧力或いは研磨荷重）を加えた状態で研磨定盤を回し、研磨液と金属膜の凸部との機械的摩擦によって凸部の金属膜を除去するものである。
【０００５】
ＣＭＰに用いられる金属用研磨液は、一般には酸化剤及び固体砥粒からなっており必要に応じてさらに酸化金属溶解剤、金属防食剤が添加される。まず酸化によって金属膜表面を酸化し、その酸化層を固体砥粒によって削り取るのが基本的なメカニズムと考えられている。凹部の金属表面の酸化層は研磨パッドにあまり触れず、固体砥粒による削り取りの効果が及ばないので、ＣＭＰの進行とともに凸部の金属層が除去されて基体表面は平坦化される。この詳細についてはジャ−ナル・オブ・エレクトロケミカルソサエティ誌（Journal of Electrochemical Society）の第１３８巻１１号（１９９１年発行）の３４６０〜３４６４頁に開示されている。
【０００６】
ＣＭＰによる研磨速度を高める方法として酸化金属溶解剤を添加することが有効とされている。固体砥粒によって削り取られた金属酸化物の粒を研磨液に溶解させてしまうと固体砥粒による削り取りの効果が増すためであると解釈できる。但し、凹部の金属膜表面の酸化層も溶解（エッチング）されて金属膜表面が露出すると、酸化剤によって金属膜表面がさらに酸化され、これが繰り返されると凹部の金属膜のエッチングが進行してしまい、平坦化効果が損なわれることが懸念される。これを防ぐためにさらに金属防食剤が添加される。平坦化特性を維持するためには、酸化金属溶解剤と金属防食剤の効果のバランスを取ることが重要であり、凹部の金属膜表面の酸化層はあまりエッチングされず、削り取られた酸化層の粒が効率良く溶解されＣＭＰによる研磨速度が大きいことが望ましい。
【０００７】
このように酸化金属溶解剤と金属防食剤を添加して化学反応の効果を加えることにより、ＣＭＰによる研磨速度が向上すると共に、ＣＭＰされる金属層表面の損傷（ダメ−ジ）も低減される効果が得られる。
【０００８】
しかしながら、従来のＣＭＰによる埋め込み配線形成は、（１）埋め込まれた金属配線の表面中央部分が等方的に腐食されて皿の様に窪む現象（ディッシング）の発生、配線密度の高い部分で絶縁膜も研磨されて金属配線の厚みが薄くなる現象（エロージョン或いはシニング）の発生、（２）研磨傷（スクラッチ）の発生、（３）研磨後の基体表面に残留する研磨カスを除去するための洗浄プロセスが複雑であること、（４）廃液処理に起因するコストアップ、（５）金属の腐食、等の問題が生じる。
【０００９】
ディッシングや研磨中の銅合金の腐食を抑制し、信頼性の高いＬＳＩ配線を形成するために、グリシン等のアミノ酢酸又はアミド硫酸からなる酸化金属溶解剤及びＢＴＡ（ベンゾトリアゾ−ル）を含有する金属用研磨液を用いる方法が提唱されている。この技術は例えば特開平８−８３７８０号公報に記載されている。
【００１０】
銅または銅合金のダマシン配線形成やタングステン等のプラグ配線形成等の金属埋め込み形成においては、埋め込み部分以外に形成される層間絶縁膜である２酸化シリコン膜の研磨速度も大きい場合には、層間絶縁膜ごと配線の厚みが薄くなるエロージョンが発生する。その結果、配線抵抗の増加やパターン密度等により抵抗のばらつきが生じるために、研磨される金属膜に対して二酸化シリコン膜の研磨速度が十分小さい特性が要求される。そこで、酸の解離により生ずる陰イオンにより二酸化シリコンの研磨速度を抑制するため、研磨液のｐＨをｐＫａ−０．５よりも大きくする方法が提唱されている。この技術は、例えば特許第２８１９１９６号公報に記載されている。
【００１１】
一方、配線の銅或いは銅合金等の下層には、層間絶縁膜中への銅拡散防止のためにバリア層として、タングステンや窒化タングステン及びタングステン合金やその他のタングステン化合物等が形成される。したがって、銅或いは銅合金を埋め込む配線部分以外では、露出したバリア層をＣＭＰにより取り除く必要がある。しかし、これらのバリア層導体膜は、銅或いは銅合金に比べ硬度が高いために、銅または銅合金用の研磨材料の組み合わせでは十分なＣＭＰ速度が得られず、バリア層をＣＭＰにより取り除く間に銅または銅合金等がエッチングされ配線厚さが低下するという問題が生じる。
【００１２】
【発明が解決しようとする課題】
本発明の目的は、金属の研磨速度が大きくエッチング速度が小さいため、生産性が高く、ディッシング及びエロージョンが小さい金属用研磨液を提供することにあり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの製造に好適な金属用研磨液を提供することにある。
本発明の他の目的は、上記の発明の効果に加え、さらに金属の腐食が小さい金属用研磨液を提供することにあり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの製造に好適な金属用研磨液を提供することにある。
本発明の他の目的は、上記の発明の効果に加え、さらに研磨速度が大きい金属用研磨液を提供することにあり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの製造に好適な金属用研磨液を提供することにある。
本発明の他の目的は、上記の発明の効果に加え、さらに研磨速度が大きい金属用研磨液を提供することにあり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの製造に好適な金属用研磨液を提供することにある。
本発明の他の目的は、上記の発明の効果に加え、さらに生産性が高くディッシング及びエロージョンが小さい金属用研磨液を提供することにあり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの製造に好適な金属用研磨液を提供することにある。
本発明の他の目的は、上記の発明の効果に加え、さらに研磨の面内均一性が高い金属用研磨液を提供することにあり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの製造に好適な金属用研磨液を提供することにある。
本発明の他の目的は、上記の発明の効果に加え、さらに研磨の面内均一性が高い金属用研磨液を提供することにあり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの製造に好適な金属用研磨液を提供することにある。
本発明の他の目的は、上記の発明の効果に加え、さらに研磨傷（スクラッチ）が少なく、研磨後の基体表面に残留する研磨カスが少ない金属用研磨液を提供することにあり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの製造に好適な金属用研磨液を提供することにある。
本発明の他の目的は、銅、銅合金及び銅又は銅合金の酸化物用として、上記の発明の効果を有する金属用研磨液を提供することにあり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの製造に好適な金属用研磨液を提供することにある。
本発明の他の目的は、タングステン、窒化タングステン、タングステン合金、その他のタングステン化合物等のバリア層用として、上記の発明の効果を有する金属用研磨液を提供することにあり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの製造に好適な金属用研磨液を提供することにある。
に好適である。
本発明の他の目的は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの研磨方法を提供することにある。
本発明の他の目的は、上記の発明の効果に加え、さらに生産性に優れる半導体デバイスの研磨方法を提供することにある。
【００１３】
【課題を解決するための手段】
本発明は、酸化剤、酸化金属溶解剤、金属防食剤、及び水を含有する研磨液であり、金属防食剤がピリミジン骨格を有する化合物であることを特徴とする金属用研磨液に関する。
本発明は、上記ピリミジン骨格を有する化合物が、４−アミノピラゾロ［３，４−ｄ］ピリミジン、１，２，４−トリアゾロ［１，５−ａ］ピリミジン、２−メチル−５，７−ジフェニル−（１，２，４）トリアゾロ［１，５−ａ］ ピリミジン及び２−メチルサルファニル−５，７−ジフェニル−（１，２，４）トリアゾロ［１，５−ａ］ピリミジンから選ばれる少なくとも１種の化合物である金属用研磨液に関する。
本発明は、上記金属防食剤が、ピリミジン骨格を有する化合物とトリアゾール骨格を有する化合物とを併用することを特徴とする金属用研磨液関する。
本発明は、トリアゾール骨格を有する化合物が１，２，３−トリアゾール、１，２，４−トリアゾール、３−アミノ−１Ｈ−１，２，４−トリアゾール、ベンゾトリアゾール、１−ヒドロキシベンゾトリアゾールから選ばれる少なくとも１種の化合物である金属用研磨液に関する。
本発明は、上記金属の酸化剤が、過酸化水素、硝酸、過ヨウ素酸カリウム、次亜塩素酸及びオゾン水から選ばれる少なくとも１種の化合物である金属用研磨液に関する。
本発明は、重量平均分子量が５００以上の水溶性ポリマーを含有する上記金属用研磨液に関する。
本発明は、重量平均分子量が５００以上の水溶性ポリマーが、多糖類、ポリカルボン酸、ポリカルボン酸エステル及びそれらの塩、並びにビニル系ポリマーから選ばれた少なくとも１種のポリマーから選ばれた少なくとも１種のポリマーである上記金属用研磨液に関する。
本発明は、上記酸化金属溶解剤が、有機酸、有機酸エステル、有機酸のアンモニウム塩から選ばれる少なくとも１種の化合物である金属用研磨液に関する。
本発明は、研磨される金属が、銅、銅合金及び銅若しくは銅合金の酸化物から選ばれる少なくとも１種を含む金属である上記金属用研磨液に関する。
本発明は、研磨される金属のバリア層が、タングステン、窒化タングステン、タングステン合金、又はその他のタングステン化合物である上記金属用研磨液に関する。
本発明は、研磨定盤の研磨布上に上記金属用研磨液を供給しながら、被研磨膜を有する基板を研磨布に押圧した状態で研磨定盤と基板を相対的に動かすことによって被研磨膜を研磨することを特徴とする研磨方法に関する。
本発明は、研磨定盤の研磨布上に上記金属用研磨液を供給しながら、金属とバリア層を連続して研磨する上記研磨方法に関する。
【００１４】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明の金属用研磨液は、主要構成成分として金属の酸化剤、酸化金属溶解剤、金属防食剤、及び水からなる。
【００１５】
本発明の金属の酸化剤としては、過酸化水素（Ｈ２Ｏ２）、硝酸、過ヨウ素酸カリウム、次亜塩素酸、オゾン水等が挙げられ、その中でも過酸化水素が特に好ましい。これらは１種類単独で、若しくは２種類以上混合して用いることができる。基体が集積回路用素子を含むシリコン基板である場合、アルカリ金属、アルカリ土類金属、ハロゲン化物などによる汚染は望ましくないので、不揮発成分を含まない酸化剤が望ましい。但し、オゾン水は組成の時間変化が激しいので過酸化水素が最も適している。但し、適用対象の基体が半導体素子を含まないガラス基板などである場合は不揮発成分を含む酸化剤であっても差し支えない。
【００１６】
本発明の酸化金属溶解剤は、水溶性のものであれば特に制限はないが、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、２−メチル酪酸、ｎ−ヘキサン酸、３，３−ジメチル酪酸、２−エチル酪酸、４−メチルペンタン酸、ｎ−ヘプタン酸、２−メチルヘキサン酸、ｎ−オクタン酸、２−エチルヘキサン酸、安息香酸、グリコ−ル酸、サリチル酸、グリセリン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、マレイン酸、フタル酸、リンゴ酸、酒石酸、クエン酸等の有機酸、これらの有機酸エステル及びこれら有機酸のアンモニウム塩等が挙げられる。また塩酸、硫酸、硝酸等の無機酸、これら無機酸のアンモニウム塩類、例えば過硫酸アンモニウム、硝酸アンモニウム、塩化アンモニウム等、クロム酸等が挙げられる。これらの中では、実用的なＣＭＰ速度を維持しつつ、エッチング速度を効果的に抑制できるという点でギ酸、マロン酸、リンゴ酸、酒石酸、クエン酸が銅、銅合金及び銅若しくは銅合金の酸化物から選ばれた少なくとも１種の金属層を含む積層膜に対して好適である。これらは１種類単独で、若しくは２種類以上混合して用いることができる。
【００１７】
本発明の金属防食剤は、ピリミジン骨格を有するものであれば特に制限はなく、ピリミジン、１，２，４−トリアゾロ［１，５−ａ］ ピリミジン、１，３，６，７，８−ヘキサハイドロ−２Ｈ−ピリミド［１，２−ａ］ ピリミジン、１，３−ジフェニル−ピリミジン−２，４，６−トリオン、１，４，５，６−テトラハイドロピリミジン、２，４，５，６−テトラアミノピリミジンサルフェイト、２，４，５−トリハイドロキシピリミジン、２，４，６−トリアミノピリミジン、２，４，６−トリクロロピリミジン、２，４，６−トリメトキシピリミジン、２，４，６−トリフェニルピリミジン、２，４−ジアミノ−６−ヒドロキシルピリミジン、２，４−ジアミノピリミジン、２−アセトアミドピリミジン、２−アミノピリミジン、２−メチル−５，７−ジフェニル−（１，２，４）トリアゾロ（１，５−ａ）ピリミジン、２−メチルサルファニル−５，７−ジフェニル−（１，２，４）トリアゾロ（１，５−ａ） ピリミジン、２−メチルサルファニル−５，７−ジフェニル−４，７−ジヒドロ−（１，２，４）トリアゾロ（１，５−ａ）ピリミジン、４−アミノピラゾロ［３，４−ｄ］ ピリミジン等が挙げられ、特に、研磨速度、エッチング速度の点から４−アミノピラゾロ［３，４−ｄ］ピリミジン、１，２，４−トリアゾロ［１，５−ａ］ピリミジン、２−メチル−５，７−ジフェニル−（１，２，４）トリアゾロ［１，５−ａ］ ピリミジン、２−メチルサルファニル−５，７−ジフェニル−（１，２，４）トリアゾロ（１，５−ａ） ピリミジンが好ましい。これらは１種類単独で、若しくは２種類以上混合して用いることができる。
【００１８】
また、ピリミジン骨格を有する金属防食剤と併用するトリアゾール骨格を有する化合物としては、特に制限はないが、２−メルカプトベンゾチアゾール、１，２，３−トリアゾール、１，２，４−トリアゾール、３−アミノ−１Ｈ−１，２，４−トリアゾール、ベンゾトリアゾール、１−ヒドロキシベンゾトリアゾール、１−ジヒドロキシプロピルベンゾトリアゾール、２，３−ジカルボキシプロピルベンゾトリアゾール、４−ヒドロキシベンゾトリアゾール、４−カルボキシル（−１Ｈ−）ベンゾトリアゾール、４−カルボキシル（−１Ｈ−）ベンゾトリアゾールメチルルエステル、４−カルボキシル（−１Ｈ−）ベンゾトリアゾールブチルエステル、４−カルボキシル（−１Ｈ−）ベンゾトリアゾールオクチルエステル、５−ヘキシルベンゾトリアゾール、［１，２，３−ベンゾトリアゾリル−１−メチル］［１，２，４−トリアゾリル−１−メチル］［２−エチルヘキシル］アミン、トリルトリアゾール、ナフトトリアゾール、ビス［（１−ベンゾトリアゾリル）メチル］ホスホン酸等が挙げられる。
【００１９】
本発明において用いられる水溶性ポリマーとしては、重量平均分子量が５００以上であれば特に制限はなく、例えばアルギン酸、ペクチン酸、カルボキシメチルセルロース、寒天、カードラン及びプルラン等の多糖類；ポリアスパラギン酸、ポリグルタミン酸、ポリリシン、ポリリンゴ酸、ポリメタクリル酸、ポリメタクリル酸アンモニウム塩、ポリメタクリル酸ナトリウム塩、ポリアミド酸、ポリマレイン酸、ポリイタコン酸、ポリフマル酸、ポリ（ｐ−スチレンカルボン酸）、ポリアクリル酸、ポリアクリルアミド、アミノポリアクリルアミド、ポリアクリル酸アンモニウム塩、ポリアクリル酸ナトリウム塩、ポリアミド酸、ポリアミド酸アンモニウム塩、ポリアミド酸ナトリウム塩及びポリグリオキシル酸等のポリカルボン酸、ポリカルボン酸エステル及びそれらの塩；ポリビニルアルコ−ル、ポリビニルピロリドン及びポリアクロレイン等のビニル系ポリマー等が挙げられる。但し、適用する基体が半導体集積回路用シリコン基板などの場合はアルカリ金属、アルカリ土類金属、ハロゲン化物等による汚染は望ましくないため、酸若しくはそのアンモニウム塩が望ましい。基体がガラス基板等である場合はその限りではない。その中でもペクチン酸、寒天、ポリリンゴ酸、ポリメタクリル酸、ポリアクリル酸アンモニウム塩、ポリアクリルアミド、ポリビニルアルコール及びポリビニルピロリドン、それらのエステル及びそれらのアンモニウム塩が好ましい。
【００２０】
本発明における金属の酸化剤の配合量は、金属の酸化剤、酸化金属溶解剤、金属防食剤、水溶性ポリマー及び水の総量１００ｇに対して、０．１〜５０ｇとすることが好ましく、０．２〜４０ｇとすることがより好ましく、０．３〜３０ｇとすることが特に好ましい。配合量が０．１ｇ未満では、金属の酸化が不十分でＣＭＰ速度が低く、５０ｇを超えると、研磨面に荒れが生じる傾向がある。
【００２１】
本発明における酸化金属溶解剤成分の配合量は、金属の酸化剤、酸化金属溶解剤、金属防食剤、水溶性ポリマー及び水の総量１００ｇに対して０．００１〜１０ｇとすることが好ましく、０．０１〜８ｇとすることがより好ましく、０．０２〜５ｇとすることが特に好ましい。この配合量が０．００１ｇ未満になると研磨カスが増加する傾向にあり、１０ｇを超えると、エッチングの抑制が困難となる傾向がある。
【００２２】
本発明における金属防食剤の配合量は、金属の酸化剤、酸化金属溶解剤、金属防食剤、水溶性ポリマー及び水の総量１００ｇに対して０．００１〜１０ｇとすることが好ましく、０．０１〜８ｇとすることがより好ましく、０．０２〜５ｇとすることが特に好ましい。この配合量が０．００１未満では、エッチングの抑制が困難となる傾向があり、１０ｇを超えると研磨速度が低くなってしまう傾向がある。
【００２３】
本発明における水溶性ポリマーの配合量は、金属の酸化剤、酸化金属溶解剤、金属防食剤、水溶性ポリマ及び水の総量１００ｇに対して０〜１０ｇとすることが好ましく、０．０１〜８ｇとすることがより好ましく、０．０２〜５ｇとすることが特に好ましい。この配合量が１０ｇを超えると研磨速度が低下する傾向がある。
水溶性ポリマーの重量平均分子量は５００以上とすることが好ましく、１５００以上とすることがより好ましく５０００以上とすることが特に好ましい。重量平均分子量の上限は特に規定するものではないが、溶解性の観点から５００万以下である。重量平均分子量が５００未満では高い研磨速度が発現しない傾向にある。本発明では、重量平均分子量が５００以上である少なくとも１種以上の水溶性ポリマーを用いることが好ましい。
【００２４】
本発明の金属用研磨液には、上述した材料のほかにアルミナ、シリカ、セリア等の固体砥粒、界面活性剤、ビクトリアピュアブルー等の染料、フタロシアニングリーン等の顔料等の着色剤を含有させてもよい。
【００２５】
本発明を適用する金属としては、銅、銅合金及び銅若しくは銅合金の酸化物が挙げられ、公知のスパッタ法、メッキ法により成膜された金属膜に適用される。
【００２６】
本発明を適用する金属のバリア層としては、タングステン、窒化タングステン、タングステン合金、その他のタングステン化合物、チタン、窒化チタン、チタン合金、その他のチタン化合物、タンタル、窒化タンタル、タンタル合金、その他のタンタル化合物、から選ばれた少なくとも１種の金属バリア層を含む積層膜である。
【００２７】
本発明の研磨方法は、研磨定盤の研磨布上に前記の金属用研磨液を供給しながら、被研磨膜を有する基板を研磨布に押圧した状態で研磨定盤と基板を相対的に動かすことによって被研磨膜を研磨する研磨方法である。研磨する装置としては、半導体基板を保持するホルダと研磨布（パッド）を貼り付けた（回転数が変更可能なモータ等を取り付けてある）定盤を有する一般的な研磨装置が使用できる。研磨布としては、一般的な不織布、発泡ポリウレタン、多孔質フッ素樹脂などが使用でき、特に制限がない。研磨条件には制限はないが、定盤の回転速度は基板が飛び出さないように２００ｒｐｍ以下の低回転が好ましい。被研磨膜を有する半導体基板の研磨布への押し付け圧力が１〜１００ＫＰａであることが好ましく、ＣＭＰ速度のウエハ面内均一性及びパターンの平坦性を満足するためには、５〜５０ＫＰａであることがより好ましい。研磨している間、研磨布には金属用研磨液をポンプ等で連続的に供給する。この供給量に制限はないが、研磨布の表面が常に研磨液で覆われていることが好ましい。研磨終了後の半導体基板は、流水中でよく洗浄後、スピンドライ等を用いて半導体基板上に付着した水滴を払い落としてから乾燥させることが好ましい。
【００２８】
【実施例】
以下、実施例により本発明を説明する。本発明はこれらの実施例により限定されるものではない。
（研磨液作製方法） 表１及び表２に示すような配合で実施例１〜８及び比較例１〜２で用いる金属用研磨液を作製した。
【００２９】
【表１】
【表２】
基体：厚さ１５００ｎｍの銅金属を形成したシリコン基板
厚さ２００ｎｍのタンタル膜を形成したシリコン基板
配線溝深さ０．５μｍ／バリア層：タンタル膜厚５０ｎｍ／銅膜厚１．０μｍのパターン付き基板
研磨パッド：（ＩＣ１０００（ロデール社製））
研磨圧力：２１０ｇ／ｃｍ２（２０．５８ＫＰａ）、基体と研磨定盤との相対速度：３６ｍ／ｍｉｎ（研磨品評価項目）
研磨速度：各膜の研磨前後での膜厚差を電気抵抗値から換算して求めた。
エッチング速度：攪拌した金属用研磨液（室温、２５℃、攪拌１００ｒｐｍ）への浸漬前後の銅層膜厚差を電気抵抗値から換算して求めた。
ディッシング量：二酸化シリコン中に深さ０．５〜１００μｍの溝を形成して、公知のスパッタ法によってバリア層として厚さ５０ｎｍのタンタル膜を形成し、同様にスパッタ法により銅膜を１．０μｍ形成して公知の熱処理によって埋め込んだシリコン基板を用い、基体表面全面で二酸化シリコンが露出するまで研磨を行った。次に、触針式段差計で配線金属部幅１００μｍ、絶縁膜部幅１００μｍが交互に並んだストライプ状パターン部の表面形状から、絶縁膜部に対する配線金属部の膜減り量を求めた。
エロージョン量：上記ディッシング量評価用基体に形成された配線金属部幅４．５μｍ、絶縁膜部幅０．５μｍが交互に並んだ総幅２．５ｍｍのストライプ状パターン部の表面形状を触針式段差計により測定し、ストライプ状パターン周辺の絶縁膜フィールド部に対するパターン中央付近の絶縁膜部の膜減り量を求めた。
配線抵抗量：基体表面全面で二酸化シリコンが露出するまで研磨を行った後に、配線抵抗値の測定を行った。ディッシング量測定部の幅１００μｍ銅配線パターンにおいて、配線長さ１ｍｍの配線抵抗値を測定した。また、エロージョン量測定部の幅４．５μｍ銅配線パターンにおいて、配線長さ１ｍｍの配線抵抗値を測定した。
実施例１〜８及び比較例１〜２のＣＭＰによる研磨速度、エッチング速度、ディッシング量、エロージョン量、及び配線抵抗値を表３及び表４に示した。
【００３１】
【表３】
【表４】
比較例１では、タングステンバリア層のエッチング速度が大きいためにディッシング及びエロージョンが大きく配線抵抗値が増加している。また、比較例２では、銅金属及びタングステンバリア層のエッチング速度が大きいためにディッシング及びエロージョンが大きく配線抵抗値が増加している。それに対し実施例１〜８では、銅金属とタングステンバリア層のエッチング速度が小さいため良好なディッシング及びエロージョン特性により配線抵抗の増加が少ない。
【００３４】
【発明の効果】
本発明により、金属の研磨速度が大きくエッチング速度が小さいため、生産性が高く、ディッシング及びエロージョンが小さい金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイス及び機器に好適である。
本発明により、上記の発明の効果に加え、さらに金属の腐食が小さい金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイス及び機器に好適である。
本発明により、上記の発明の効果に加え、さらに生産性が高くディッシング及びエロージョンが小さい金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイス及び機器に好適である。
本発明により、上記の発明の効果に加え、さらに研磨の面内均一性が高い金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイス及び機器に好適である。
本発明により、上記の発明の効果に加え、さらに研磨傷（スクラッチ）が少なく、研磨後の基体表面に残留する研磨カスが少ない金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイス及び機器に好適である。
本発明により、銅、銅合金及び銅又は銅合金の酸化物用として、上記の発明の効果を有する金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイス及び機器に好適である。
本発明により、タングステン、窒化タングステン、タングステン合金、その他のタングステン化合物等のバリア層用として、上記の発明の効果を有する金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイス及び機器に好適である。
本発明により、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイスの研磨方法が得られた。
本発明により、上記の発明の効果に加え、さらに生産性に優れる半導体デバイスの研磨方法が得られた。[0001]
BACKGROUND OF THE INVENTION
In particular, the present invention relates to a metal polishing liquid suitably used in a wiring process of a semiconductor device and a polishing method using the same.
[0002]
[Prior art]
In recent years, new microfabrication techniques have been developed along with higher integration and higher performance of semiconductor integrated circuits (LSIs). The chemical mechanical polishing (CMP) method is one of them, and is a technique frequently used in the planarization of the interlayer insulating film, the formation of the metal plug, and the formation of the embedded wiring in the LSI manufacturing process, particularly in the multilayer wiring forming process. This technique is disclosed, for example, in US Pat. No. 4,944,836.
[0003]
In recent years, attempts have been made to use copper alloys as wiring materials in order to improve the performance of LSIs. However, it is difficult to finely process the copper alloy by the dry etching method frequently used in the formation of the conventional aluminum alloy wiring. Therefore, a so-called damascene method is mainly employed in which a copper alloy thin film is deposited and embedded on an insulating film in which grooves have been formed in advance, and the copper alloy thin film other than the grooves is removed by CMP to form embedded wiring. . This technique is disclosed, for example, in JP-A-2-278822.
[0004]
A general method of metal CMP is to apply a polishing pad on a circular polishing platen (platen), immerse the polishing pad surface with a metal polishing liquid, and press the surface on which the metal film of the substrate is formed. The polishing platen is rotated in a state where a predetermined pressure (polishing pressure or polishing load) is applied from the back surface, and the metal film on the convex portion is removed by mechanical friction between the polishing liquid and the convex portion of the metal film.
[0005]
The metal polishing liquid used in CMP is generally composed of an oxidizer and solid abrasive grains, and a metal oxide solubilizer and a metal anticorrosive are further added as necessary. It is considered that the basic mechanism is to first oxidize the surface of the metal film by oxidation and scrape the oxidized layer with solid abrasive grains. Since the oxide layer on the metal surface of the recess does not touch the polishing pad so much and does not have the effect of scraping off by the solid abrasive grains, the metal layer of the projection is removed and the substrate surface is flattened with the progress of CMP. The details are disclosed in Journal of Electrochemical Society, Vol. 138, No. 11 (published in 1991), pages 3460 to 3464.
[0006]
As a method for increasing the polishing rate by CMP, it is effective to add a metal oxide dissolving agent. It can be interpreted that the effect of scraping with the solid abrasive grains increases when the metal oxide grains scraped with the solid abrasive grains are dissolved in the polishing liquid. However, if the oxide layer on the surface of the metal film in the recess is dissolved (etched) and the metal film surface is exposed, the surface of the metal film is further oxidized by the oxidizing agent, and if this is repeated, the etching of the metal film in the recess proceeds. There is a concern that the flattening effect is impaired. In order to prevent this, a metal anticorrosive is further added. In order to maintain the flattening characteristics, it is important to balance the effects of the metal oxide solubilizer and the metal anticorrosive agent. The oxide layer on the metal film surface in the recess is not etched so much, and the etched oxide layer It is desirable that the grains are efficiently dissolved and the polishing rate by CMP is high.
[0007]
Thus, by adding a metal oxide solubilizer and a metal anticorrosive to add the effect of chemical reaction, the polishing rate by CMP is improved and damage (damage) on the surface of the metal layer to be CMP is also reduced. An effect is obtained.
[0008]
However, the conventional embedded wiring formation by CMP is (1) a phenomenon in which the central portion of the surface of the embedded metal wiring is isotropically corroded and becomes a dish-like recess (dishing), and the wiring density is high. In order to remove the phenomenon (erosion or thinning) that the insulating film is also polished and the metal wiring is thinned (erosion or thinning), (2) polishing scratches (scratches), and (3) polishing residue remaining on the substrate surface after polishing. (4) Cost increase caused by waste liquid treatment, (5) Corrosion of metal, and the like occur.
[0009]
Metals containing metal oxide solubilizers made of aminoacetic acid or amidosulfuric acid such as glycine and BTA (benzotriazole) to suppress corrosion of copper alloys during dishing and polishing and to form highly reliable LSI wiring A method of using a polishing liquid for the use has been proposed. This technique is described, for example, in JP-A-8-83780.
[0010]
In metal embedding formation such as damascene wiring formation of copper or copper alloy or plug wiring formation of tungsten or the like, when the polishing rate of the silicon dioxide film which is an interlayer insulating film formed other than the embedded portion is high, interlayer insulation Erosion occurs in which the thickness of the wiring is reduced with each film. As a result, resistance variation occurs due to an increase in wiring resistance, pattern density, and the like, so that a characteristic in which the polishing rate of the silicon dioxide film is sufficiently small with respect to the metal film to be polished is required. Therefore, in order to suppress the polishing rate of silicon dioxide by anions generated by acid dissociation, a method of increasing the pH of the polishing liquid to be higher than pKa-0.5 has been proposed. This technique is described in, for example, Japanese Patent No. 2819196.
[0011]
On the other hand, tungsten, tungsten nitride, a tungsten alloy, other tungsten compounds, or the like is formed as a barrier layer to prevent copper diffusion into the interlayer insulating film in the lower layer of copper or copper alloy of the wiring. Therefore, it is necessary to remove the exposed barrier layer by CMP except for the wiring portion in which copper or copper alloy is embedded. However, since these barrier layer conductor films have higher hardness than copper or copper alloy, a sufficient CMP rate cannot be obtained by a combination of polishing materials for copper or copper alloy, and the barrier layer is removed by CMP. A problem arises in that copper or copper alloy or the like is etched to reduce the wiring thickness.
[0012]
[Problems to be solved by the invention]
An object of the present invention is to provide a metal polishing liquid having high productivity and low dishing and erosion because the metal polishing rate is high and the etching rate is low, and miniaturization, thinning, dimensional accuracy, and electrical characteristics are provided. An object of the present invention is to provide a metal polishing slurry that is excellent in manufacturing a highly reliable semiconductor device.
Another object of the present invention is to provide a metal-polishing liquid that has further reduced metal corrosion in addition to the effects of the above-described invention, and is excellent in miniaturization, thinning, dimensional accuracy, electrical characteristics, and reliability. An object of the present invention is to provide a metal-polishing liquid suitable for manufacturing a high-semiconductor device.
Another object of the present invention is to provide a metal polishing liquid having a higher polishing rate in addition to the effects of the above-described invention, and is excellent in miniaturization, thinning, dimensional accuracy, electrical characteristics, and high reliability. An object of the present invention is to provide a metal polishing liquid suitable for manufacturing semiconductor devices.
Another object of the present invention is to provide a metal polishing liquid having a higher polishing rate in addition to the effects of the above-described invention, and is excellent in miniaturization, thinning, dimensional accuracy, electrical characteristics, and high reliability. An object of the present invention is to provide a metal polishing liquid suitable for manufacturing semiconductor devices.
Another object of the present invention is to provide a metal polishing liquid with high productivity and low dishing and erosion, in addition to the effects of the above-described invention, and is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics. Another object of the present invention is to provide a metal polishing slurry suitable for manufacturing a highly reliable semiconductor device.
Another object of the present invention is to provide a metal polishing liquid having high in-plane uniformity of polishing, in addition to the effects of the above-described invention, and is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, An object of the present invention is to provide a metal polishing slurry suitable for manufacturing a highly reliable semiconductor device.
Another object of the present invention is to provide a metal polishing liquid having high in-plane uniformity of polishing, in addition to the effects of the above-described invention, and is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, An object of the present invention is to provide a metal polishing slurry suitable for manufacturing a highly reliable semiconductor device.
Another object of the present invention is to provide a metal-polishing liquid with less polishing scratches (scratches) and less polishing residue remaining on the polished substrate surface in addition to the effects of the above-described invention. An object of the present invention is to provide a metal-polishing liquid that is excellent in thin film formation, dimensional accuracy, and electrical characteristics, and suitable for manufacturing a highly reliable semiconductor device.
Another object of the present invention is to provide a metal-polishing liquid having the effects of the above-described invention for copper, copper alloy and copper or copper alloy oxide. An object of the present invention is to provide a metal-polishing liquid that is excellent in electrical characteristics and suitable for manufacturing a highly reliable semiconductor device.
Another object of the present invention is to provide a metal-polishing liquid having the effects of the above-mentioned invention as a barrier layer for tungsten, tungsten nitride, tungsten alloy, other tungsten compounds, etc. Another object of the present invention is to provide a metal polishing liquid that is excellent in dimensional accuracy and electrical characteristics and suitable for manufacturing a highly reliable semiconductor device.
It is suitable for.
Another object of the present invention is to provide a highly reliable semiconductor device polishing method that is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics.
Another object of the present invention is to provide a method for polishing a semiconductor device that is excellent in productivity in addition to the effects of the above-described invention.
[0013]
[Means for Solving the Problems]
The present invention relates to a polishing liquid containing an oxidizing agent, a metal oxide dissolving agent, a metal anticorrosive, and water, wherein the metal anticorrosive is a compound having a pyrimidine skeleton.
In the present invention, the compound having the pyrimidine skeleton is 4-aminopyrazolo [3,4-d] pyrimidine, 1,2,4-triazolo [1,5-a] pyrimidine, 2-methyl-5,7-diphenyl- At least one selected from (1,2,4) triazolo [1,5-a] pyrimidine and 2-methylsulfanyl-5,7-diphenyl- (1,2,4) triazolo [1,5-a] pyrimidine. The present invention relates to a metal polishing slurry which is a seed compound.
The present invention relates to a metal polishing slurry, wherein the metal anticorrosive agent uses a compound having a pyrimidine skeleton and a compound having a triazole skeleton in combination.
In the present invention, the compound having a triazole skeleton is selected from 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, benzotriazole, and 1-hydroxybenzotriazole. It is related with the metal-polishing liquid which is the at least 1 sort (s) of compound.
The present invention relates to a metal polishing slurry, wherein the metal oxidizing agent is at least one compound selected from hydrogen peroxide, nitric acid, potassium periodate, hypochlorous acid, and ozone water.
The present invention relates to the above metal polishing slurry containing a water-soluble polymer having a weight average molecular weight of 500 or more.
In the present invention, the water-soluble polymer having a weight average molecular weight of 500 or more is at least selected from at least one polymer selected from polysaccharides, polycarboxylic acids, polycarboxylic acid esters and salts thereof, and vinyl polymers. It is related with the said metal polishing liquid which is 1 type of polymer.
The present invention relates to a metal polishing slurry, wherein the metal oxide solubilizer is at least one compound selected from organic acids, organic acid esters, and ammonium salts of organic acids.
The present invention relates to the above polishing liquid for metal, wherein the metal to be polished is a metal containing at least one selected from copper, copper alloys, and copper or copper alloy oxides.
The present invention relates to the above metal polishing liquid, wherein the metal barrier layer to be polished is tungsten, tungsten nitride, tungsten alloy, or other tungsten compounds.
The present invention provides a polishing target by moving the polishing surface plate and the substrate relatively while pressing the substrate having the film to be polished against the polishing cloth while supplying the metal polishing liquid onto the polishing cloth of the polishing surface plate. The present invention relates to a polishing method characterized by polishing a film.
The present invention relates to the above polishing method for continuously polishing a metal and a barrier layer while supplying the metal polishing liquid onto a polishing cloth of a polishing surface plate.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The metal polishing liquid of the present invention comprises a metal oxidizer, a metal oxide solubilizer, a metal anticorrosive, and water as main components.
[0015]
As the metal oxidizing agent of the present invention, hydrogen peroxide (H 2 O 2 ), Nitric acid, potassium periodate, hypochlorous acid, ozone water, etc., among which hydrogen peroxide is particularly preferred. These may be used alone or in combination of two or more. When the substrate is a silicon substrate including an integrated circuit element, contamination by alkali metal, alkaline earth metal, halide, etc. is not desirable, so an oxidizing agent that does not contain a nonvolatile component is desirable. However, hydrogen peroxide is most suitable because ozone water has a severe compositional change over time. However, when the substrate to be applied is a glass substrate or the like that does not include a semiconductor element, an oxidizing agent that includes a nonvolatile component may be used.
[0016]
The metal oxide solubilizer of the present invention is not particularly limited as long as it is water-soluble, but formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, Examples thereof include organic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid and citric acid, organic acid esters thereof, and ammonium salts of these organic acids. Further, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and ammonium salts of these inorganic acids, for example, ammonium persulfate, ammonium nitrate, ammonium chloride and the like, chromic acid and the like can be mentioned. Among these, formic acid, malonic acid, malic acid, tartaric acid, and citric acid are copper, copper alloys, and oxidation of copper or copper alloys in that the etching rate can be effectively suppressed while maintaining a practical CMP rate. It is suitable for a laminated film including at least one metal layer selected from those. These may be used alone or in combination of two or more.
[0017]
The metal anticorrosive of the present invention is not particularly limited as long as it has a pyrimidine skeleton. Pyrimidine, 1,2,4-triazolo [1,5-a] pyrimidine, 1,3,6,7,8-hexa Hydro-2H-pyrimido [1,2-a] pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5,6- Tetraaminopyrimidine sulfate, 2,4,5-trihydroxypyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2,4,6 -Triphenylpyrimidine, 2,4-diamino-6-hydroxylpyrimidine, 2,4-diaminopyrimidine, 2-acetamidopyrimidine, 2-aminopyrimidine, 2- Tyl-5,7-diphenyl- (1,2,4) triazolo (1,5-a) pyrimidine, 2-methylsulfanyl-5,7-diphenyl- (1,2,4) triazolo (1,5- a) Pyrimidine, 2-methylsulfanyl-5,7-diphenyl-4,7-dihydro- (1,2,4) triazolo (1,5-a) pyrimidine, 4-aminopyrazolo [3,4-d] pyrimidine In particular, 4-aminopyrazolo [3,4-d] pyrimidine, 1,2,4-triazolo [1,5-a] pyrimidine, 2-methyl-5,7 in terms of polishing rate and etching rate. -Diphenyl- (1,2,4) triazolo [1,5-a] pyrimidine, 2-methylsulfanyl-5,7-diphenyl- (1,2,4) triazolo (1,5-a) pyrimidine is preferred . These may be used alone or in combination of two or more.
[0018]
Further, the compound having a triazole skeleton used in combination with the metal anticorrosive having a pyrimidine skeleton is not particularly limited, but 2-mercaptobenzothiazole, 1,2,3-triazole, 1,2,4-triazole, 3- Amino-1H-1,2,4-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxyl (-1H -) Benzotriazole, 4-carboxyl (-1H-) benzotriazole methyl ester, 4-carboxyl (-1H-) benzotriazole butyl ester, 4-carboxyl (-1H-) benzotriazole octyl ester, 5-hexylbe Zotriazole, [1,2,3-benzotriazolyl-1-methyl] [1,2,4-triazolyl-1-methyl] [2-ethylhexyl] amine, tolyltriazole, naphthotriazole, bis [(1- Benzotriazolyl) methyl] phosphonic acid and the like.
[0019]
The water-soluble polymer used in the present invention is not particularly limited as long as the weight average molecular weight is 500 or more. For example, polysaccharides such as alginic acid, pectic acid, carboxymethylcellulose, agar, curdlan and pullulan; polyaspartic acid, poly Glutamic acid, polylysine, polymalic acid, polymethacrylic acid, polymethacrylic acid ammonium salt, polymethacrylic acid sodium salt, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid), polyacrylic acid, polyacrylamide Aminopolyacrylamide, polyacrylic acid ammonium salt, polyacrylic acid sodium salt, polyamic acid, polyamic acid ammonium salt, polyamic acid sodium salt and polyglyoxylic acid Bon acid esters and salts thereof; polyvinyl alcohol - le, vinyl polymers such as polyvinyl pyrrolidone and acrolein and the like. However, when the substrate to be applied is a silicon substrate for a semiconductor integrated circuit or the like, contamination with an alkali metal, an alkaline earth metal, a halide or the like is not desirable, and therefore an acid or an ammonium salt thereof is desirable. This is not the case when the substrate is a glass substrate or the like. Among these, pectinic acid, agar, polymalic acid, polymethacrylic acid, ammonium polyacrylate, polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone, esters thereof and ammonium salts thereof are preferable.
[0020]
The compounding amount of the metal oxidizer in the present invention is preferably 0.1 to 50 g with respect to 100 g of the total amount of metal oxidizer, metal oxide solubilizer, metal anticorrosive, water-soluble polymer and water. It is more preferable to set it as 2-40g, and it is especially preferable to set it as 0.3-30g. If the blending amount is less than 0.1 g, metal oxidation is insufficient and the CMP rate is low, and if it exceeds 50 g, the polished surface tends to be rough.
[0021]
The compounding amount of the metal oxide solubilizer component in the present invention is preferably 0.001 to 10 g with respect to 100 g of the total amount of metal oxidizer, metal oxide solubilizer, metal anticorrosive, water-soluble polymer and water. More preferably, the content is 0.01 to 8 g, and particularly preferably 0.02 to 5 g. When this amount is less than 0.001 g, polishing residue tends to increase, and when it exceeds 10 g, it is difficult to suppress etching.
[0022]
The compounding amount of the metal anticorrosive in the present invention is preferably 0.001 to 10 g with respect to 100 g of the total amount of metal oxidizer, metal oxide solubilizer, metal anticorrosive, water-soluble polymer and water, 0.01 It is more preferable to set it as -8g, and it is especially preferable to set it as 0.02-5g. When the amount is less than 0.001, it is difficult to suppress etching, and when it exceeds 10 g, the polishing rate tends to be low.
[0023]
The blending amount of the water-soluble polymer in the present invention is preferably 0 to 10 g with respect to 100 g of the total amount of metal oxidizer, metal oxide solubilizer, metal anticorrosive, water-soluble polymer and water, and 0.01 to 8 g. Is more preferable, and 0.02 to 5 g is particularly preferable. If this amount exceeds 10 g, the polishing rate tends to decrease.
The weight average molecular weight of the water-soluble polymer is preferably 500 or more, more preferably 1500 or more, and particularly preferably 5000 or more. The upper limit of the weight average molecular weight is not particularly specified, but is 5 million or less from the viewpoint of solubility. When the weight average molecular weight is less than 500, a high polishing rate tends not to be exhibited. In the present invention, it is preferable to use at least one water-soluble polymer having a weight average molecular weight of 500 or more.
[0024]
In addition to the materials described above, the metal polishing slurry of the present invention contains solid abrasives such as alumina, silica, and ceria, surfactants, dyes such as Victoria Pure Blue, and colorants such as pigments such as phthalocyanine green. May be.
[0025]
Examples of the metal to which the present invention is applied include copper, a copper alloy, and an oxide of copper or a copper alloy, which are applied to a metal film formed by a known sputtering method or plating method.
[0026]
Metal barrier layers to which the present invention is applied include tungsten, tungsten nitride, tungsten alloys, other tungsten compounds, titanium, titanium nitride, titanium alloys, other titanium compounds, tantalum, tantalum nitride, tantalum alloys, and other tantalum compounds. A laminated film including at least one metal barrier layer selected from the above.
[0027]
The polishing method of the present invention moves the polishing platen and the substrate relatively while pressing the substrate having the film to be polished against the polishing cloth while supplying the metal polishing liquid onto the polishing cloth of the polishing platen. This is a polishing method for polishing the film to be polished. As a polishing apparatus, a general polishing apparatus having a holder for holding a semiconductor substrate and a surface plate to which a polishing cloth (pad) is attached (a motor or the like whose rotation speed can be changed) is attached. As an abrasive cloth, a general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used, and there is no restriction | limiting in particular. The polishing conditions are not limited, but the rotation speed of the surface plate is preferably a low rotation of 200 rpm or less so that the substrate does not jump out. The pressure applied to the polishing cloth of the semiconductor substrate having the film to be polished is preferably 1 to 100 KPa, and 5 to 50 KPa in order to satisfy the uniformity in the wafer surface of the CMP rate and the flatness of the pattern. Is more preferable. During polishing, a polishing solution for metal is continuously supplied to the polishing cloth with a pump or the like. Although there is no restriction | limiting in this supply amount, it is preferable that the surface of polishing cloth is always covered with polishing liquid. The semiconductor substrate after completion of polishing is preferably washed in running water and then dried after removing water droplets adhering to the semiconductor substrate using spin drying or the like.
[0028]
【Example】
Hereinafter, the present invention will be described by way of examples. The present invention is not limited to these examples.
(Polishing liquid preparation method) The metal polishing liquid used by Examples 1-8 and Comparative Examples 1-2 by the mixing | blending as shown in Table 1 and Table 2 was produced.
[0029]
[Table 1]
[Table 2]
Base: silicon substrate on which copper metal with a thickness of 1500 nm is formed
Silicon substrate on which a tantalum film having a thickness of 200 nm is formed
Wiring groove depth 0.5 μm / barrier layer: patterned substrate with tantalum film thickness 50 nm / copper film thickness 1.0 μm
Polishing pad: (IC1000 (Rodel))
Polishing pressure: 210 g / cm 2 (20.58 KPa), relative speed between substrate and polishing surface plate: 36 m / min (polishing product evaluation item)
Polishing speed: The film thickness difference before and after polishing of each film was calculated from the electric resistance value.
Etching rate: The copper layer thickness difference before and after immersion in the stirred metal polishing liquid (room temperature, 25 ° C., stirring 100 rpm) was calculated from the electrical resistance value.
Dishing amount: A groove having a depth of 0.5 to 100 μm is formed in silicon dioxide, and a tantalum film having a thickness of 50 nm is formed as a barrier layer by a known sputtering method. Similarly, a copper film is formed by 1.0 μm by sputtering. Polishing was performed using a silicon substrate formed and embedded by a known heat treatment until silicon dioxide was exposed on the entire surface of the substrate. Next, the film reduction amount of the wiring metal part with respect to the insulating film part was obtained from the surface shape of the stripe pattern part in which the wiring metal part width of 100 μm and the insulating film part width of 100 μm were alternately arranged with a stylus step meter.
Erosion amount: The surface shape of the stripe pattern portion having a total width of 2.5 mm in which the wiring metal portion width of 4.5 μm and the insulating film portion width of 0.5 μm are alternately arranged on the dishing amount evaluation base is a stylus type Measured with a step gauge, the amount of film loss of the insulating film portion near the center of the pattern relative to the insulating film field portion around the stripe pattern was determined.
Wiring resistance amount: Polishing was performed until silicon dioxide was exposed on the entire surface of the substrate, and then the wiring resistance value was measured. A wiring resistance value of a wiring length of 1 mm was measured in a copper wiring pattern having a width of 100 μm in the dishing amount measuring section. Moreover, the wiring resistance value of the wiring length of 1 mm was measured in the 4.5 μm wide copper wiring pattern of the erosion amount measuring part.
Tables 3 and 4 show the polishing rate, etching rate, dishing amount, erosion amount, and wiring resistance value by CMP of Examples 1 to 8 and Comparative Examples 1 and 2.
[0031]
[Table 3]
[Table 4]
In Comparative Example 1, since the etching rate of the tungsten barrier layer is high, dishing and erosion are large and the wiring resistance value is increased. Further, in Comparative Example 2, since the etching rate of the copper metal and tungsten barrier layers is high, dishing and erosion are large and the wiring resistance value is increased. On the other hand, in Examples 1-8, since the etching rate of a copper metal and a tungsten barrier layer is small, there is little increase in wiring resistance by favorable dishing and erosion characteristics.
[0034]
【Effect of the invention】
According to the present invention, a metal polishing liquid having high productivity and low dishing and erosion was obtained because the metal polishing rate was high and the etching rate was low. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, and is suitable for highly reliable semiconductor devices and equipment.
According to the present invention, in addition to the effects of the above-described invention, a metal-polishing liquid with further reduced metal corrosion was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, and is suitable for highly reliable semiconductor devices and equipment.
According to the present invention, in addition to the effects of the above-described invention, a metal polishing liquid with higher productivity and less dishing and erosion was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, and is suitable for highly reliable semiconductor devices and equipment.
According to the present invention, in addition to the effects of the above-described invention, a metal polishing liquid with higher in-plane uniformity of polishing was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, and is suitable for highly reliable semiconductor devices and equipment.
According to the present invention, in addition to the effects of the above-described invention, a metal-polishing liquid with fewer polishing scratches (scratches) and less polishing residue remaining on the polished substrate surface was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, and is suitable for highly reliable semiconductor devices and equipment.
By this invention, the metal polishing liquid which has the effect of said invention was obtained for copper, a copper alloy, and the oxide of copper or a copper alloy. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, and is suitable for highly reliable semiconductor devices and equipment.
According to the present invention, a metal-polishing liquid having the effects of the above-described invention was obtained for barrier layers of tungsten, tungsten nitride, tungsten alloys, other tungsten compounds, and the like. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, and is suitable for highly reliable semiconductor devices and equipment.
According to the present invention, a highly reliable semiconductor device polishing method having excellent miniaturization, thinning, dimensional accuracy, and electrical characteristics has been obtained.
According to the present invention, in addition to the effects of the above-described invention, a method for polishing a semiconductor device that is further excellent in productivity was obtained.
Claims (9)
前記金属防食剤が４−アミノピラゾロ［３，４−ｄ］ピリミジン、１，２，４−トリアゾロ［１，５−ａ］ピリミジン及び２−メチル−５，７−ジフェニル−（１，２，４）トリアゾロ［１，５−ａ］ ピリミジンから選ばれる少なくとも１種のピリミジン骨格を有する化合物を含有し、
前記酸化金属溶解剤が、有機酸及び有機酸のアンモニウム塩から選ばれる少なくとも１種の化合物を含有することを特徴とする金属用研磨液。A polishing liquid containing hydrogen peroxide, a metal oxide solubilizer, a metal anticorrosive, and water,
The metal anticorrosive is 4-aminopyrazolo [3,4-d] pyrimidine, 1,2,4-triazolo [1,5-a] pyrimidine and 2-methyl-5,7-diphenyl- (1,2,4). triazolo containing [1,5-a] pyrimidine down or we compound having at least one pyrimidine skeleton selected,
A metal polishing slurry, wherein the metal oxide solubilizer contains at least one compound selected from organic acids and ammonium salts of organic acids.
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| EP2194570A1 (en) * | 1998-12-28 | 2010-06-09 | Hitachi Chemical Co., Ltd. | Materials for polishing liquid for metal, polishing liquid for metal, mehtod for preparation thereof and polishing method using the same |
| WO2003094216A1 (en) * | 2002-04-30 | 2003-11-13 | Hitachi Chemical Co., Ltd. | Polishing fluid and polishing method |
| KR100480797B1 (en) * | 2002-07-26 | 2005-04-07 | 엘지.필립스 엘시디 주식회사 | Etching solution to improve etch rate for copper molybdenum multilayers and etching method using the same |
| AU2003242397A1 (en) | 2003-06-13 | 2005-01-04 | Hitachi Chemical Co., Ltd. | Polishing fluid for metal and polishing method |
| US7384871B2 (en) * | 2004-07-01 | 2008-06-10 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing compositions and methods relating thereto |
| US7303993B2 (en) * | 2004-07-01 | 2007-12-04 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing compositions and methods relating thereto |
| KR100601740B1 (en) | 2005-04-11 | 2006-07-18 | 테크노세미켐 주식회사 | Etchant for ito & izo thin film |
| JP4658825B2 (en) * | 2006-02-23 | 2011-03-23 | 富士フイルム株式会社 | Polishing liquid for metal |
| JP4992826B2 (en) * | 2008-06-02 | 2012-08-08 | 日立化成工業株式会社 | Polishing liquid and polishing method |
| JP5088352B2 (en) * | 2009-08-24 | 2012-12-05 | 日立化成工業株式会社 | Polishing liquid for metal and polishing method |
| EP3969639A1 (en) | 2019-05-13 | 2022-03-23 | Ecolab Usa Inc. | 1,2,4-triazolo[1,5-a] pyrimidine derivative as copper corrosion inhibitor |
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| JPS604273B2 (en) * | 1979-05-25 | 1985-02-02 | 日東紡績株式会社 | Metal corrosion suppression method |
| JPS57152476A (en) * | 1981-03-14 | 1982-09-20 | Chiyoda Kagaku Kenkyusho:Kk | Corrosion inhibitor |
| JP3970439B2 (en) * | 1997-10-31 | 2007-09-05 | 株式会社ルネサステクノロジ | Manufacturing method of semiconductor device |
| JP2000133621A (en) * | 1998-10-27 | 2000-05-12 | Tokyo Magnetic Printing Co Ltd | Composition for chemical mechanical polishing |
| JP4816836B2 (en) * | 1998-12-28 | 2011-11-16 | 日立化成工業株式会社 | Polishing liquid for metal and polishing method using the same |
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