JP6362385B2 - Substrate manufacturing method and polishing composition - Google Patents
Substrate manufacturing method and polishing composition Download PDFInfo
- Publication number
- JP6362385B2 JP6362385B2 JP2014078150A JP2014078150A JP6362385B2 JP 6362385 B2 JP6362385 B2 JP 6362385B2 JP 2014078150 A JP2014078150 A JP 2014078150A JP 2014078150 A JP2014078150 A JP 2014078150A JP 6362385 B2 JP6362385 B2 JP 6362385B2
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- JP
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- Prior art keywords
- polishing
- acid
- pad
- substrate
- polishing composition
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims description 287
- 239000000758 substrate Substances 0.000 title claims description 79
- 239000000203 mixture Substances 0.000 title claims description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000007788 liquid Substances 0.000 claims description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- 239000008119 colloidal silica Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 10
- 239000006061 abrasive grain Substances 0.000 description 48
- 150000003839 salts Chemical class 0.000 description 41
- 239000002253 acid Substances 0.000 description 37
- -1 sulfonic acid compound Chemical class 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011148 porous material Substances 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 13
- 229910052783 alkali metal Inorganic materials 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002738 chelating agent Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
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- 239000000126 substance Substances 0.000 description 8
- 150000007514 bases Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
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- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
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- 229910018536 Ni—P Inorganic materials 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 150000003460 sulfonic acids Chemical class 0.000 description 5
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- 230000009467 reduction Effects 0.000 description 4
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 3
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- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
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- 238000010494 dissociation reaction Methods 0.000 description 3
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- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 3
- 229960002989 glutamic acid Drugs 0.000 description 3
- 235000013922 glutamic acid Nutrition 0.000 description 3
- 239000004220 glutamic acid Substances 0.000 description 3
- 229960004275 glycolic acid Drugs 0.000 description 3
- 229940093915 gynecological organic acid Drugs 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000008040 ionic compounds Chemical class 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 229960003330 pentetic acid Drugs 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 description 2
- SFRLSTJPMFGBDP-UHFFFAOYSA-N 1,2-diphosphonoethylphosphonic acid Chemical compound OP(O)(=O)CC(P(O)(O)=O)P(O)(O)=O SFRLSTJPMFGBDP-UHFFFAOYSA-N 0.000 description 2
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 2
- OOOLSJAKRPYLSA-UHFFFAOYSA-N 2-ethyl-2-phosphonobutanedioic acid Chemical compound CCC(P(O)(O)=O)(C(O)=O)CC(O)=O OOOLSJAKRPYLSA-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- MYWGVBFSIIZBHJ-UHFFFAOYSA-N 4-phosphonobutane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)CP(O)(O)=O MYWGVBFSIIZBHJ-UHFFFAOYSA-N 0.000 description 2
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
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- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Mechanical Treatment Of Semiconductor (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
- Grinding-Machine Dressing And Accessory Apparatuses (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本発明は、基板の製造方法および該製造方法に用いられる研磨用組成物に関する。 The present invention relates to a method for producing a substrate and a polishing composition used in the production method.
磁気ディスク基板や半導体基板など高精度な表面が要求される基板の製造プロセスには、一般に、研磨パッドを用いて被研磨物を研磨する工程が含まれる。このような研磨工程は、通常、例えばコロイダルシリカ等の砥粒を含む研磨用組成物（研磨スラリー）を被研磨物に供給して行われる。研磨パッドとしては、典型的には、パッドドレッシングにより所望の表面（研磨面）に調整したものが好ましく利用されている。この種の研磨パッドは、さらにダミー研磨により該表面を安定化した後、研磨対象である基板の研磨に利用される。コロイダルシリカ砥粒を含む研磨スラリーと研磨パッドの使用を開示する技術文献としては特許文献１〜５が挙げられる。ダミー研磨に関連する技術文献としては特許文献６が挙げられる。 A substrate manufacturing process that requires a highly accurate surface such as a magnetic disk substrate or a semiconductor substrate generally includes a step of polishing an object to be polished using a polishing pad. Such a polishing step is usually performed by supplying a polishing composition (polishing slurry) containing abrasive grains such as colloidal silica to the object to be polished. As the polishing pad, typically, a pad adjusted to a desired surface (polishing surface) by pad dressing is preferably used. This type of polishing pad is used for polishing a substrate to be polished after the surface is further stabilized by dummy polishing. Patent documents 1-5 are mentioned as technical literature which discloses use of a polishing slurry containing a colloidal silica abrasive grain, and a polishing pad. Patent Document 6 is cited as a technical document related to dummy polishing.
研磨パッドの表面状態は基板表面に転写され得ることから、基板表面のさらなる高精度化のためには、パッド表面の平滑化が欠かせない。特に、微小うねりが低減した基板表面を実現するためには、パッド表面をより平滑化させることが重要である。しかし、例えば上述のパッドドレッシング処理等によって良好に調整されたパッド表面の状態（平滑性、毛羽立ち等）は通常、その後の研磨にともない経時的に変化してしまう。良好な表面状態を維持することは難しく、そのため、微小うねりのコントロールには限度があった。 Since the surface state of the polishing pad can be transferred to the substrate surface, smoothing the pad surface is indispensable for further increasing the accuracy of the substrate surface. In particular, in order to realize a substrate surface with reduced microwaviness, it is important to make the pad surface smoother. However, the state (smoothness, fluffing, etc.) of the pad surface that is well adjusted by, for example, the above-described pad dressing process or the like usually changes with time with subsequent polishing. It is difficult to maintain a good surface condition, and therefore there is a limit to control of microwaviness.
このような状況下、本発明者らは、微小うねりを低減し得る有用な手段を見つけるために、研磨パッドのパッドドレッシング工程、ダミー研磨工程、本研磨工程と分けて段階的に要因を解析した結果、コロイダルシリカ砥粒を含む研磨液を用いる研磨において、研磨中にコロイダルシリカがパッド表面に吸着して、シリカコーティングともいうべき硬質薄膜となって、基板表面のうねり低減を阻害していることを知得した。この知見に基づき、さらに検討を進めた結果、コロイダルシリカのパッド表面への吸着を制限し得る手段を見出し、本発明を完成するに至った。すなわち、本発明は、微小うねりを低減し得る基板の製造方法を提供することを目的とする。本発明の他の目的は、上記製造方法に用いられる研磨用組成物を提供することである。 Under such circumstances, the present inventors analyzed the factors step by step separately from the pad dressing process of the polishing pad, the dummy polishing process, and the main polishing process in order to find a useful means that can reduce microwaviness. As a result, in polishing using a polishing liquid containing colloidal silica abrasive grains, colloidal silica is adsorbed on the pad surface during polishing to form a hard thin film that can also be referred to as silica coating, which inhibits the reduction of waviness on the substrate surface. I knew. As a result of further investigation based on this knowledge, a means capable of limiting the adsorption of colloidal silica to the pad surface was found, and the present invention was completed. That is, an object of the present invention is to provide a method for manufacturing a substrate that can reduce micro-waviness. Another object of the present invention is to provide a polishing composition used in the above production method.
本発明によると、基板の製造方法が提供される。この方法は、研磨パッドをパッドドレッシングする工程（ａ）と；前記パッドドレッシングされた研磨パッドおよび研磨液を用いてダミー研磨する工程（ｂ）と；研磨対象基板を研磨する工程（ｃ）と；を含む。そして、前記研磨液は、コロイダルシリカ砥粒とパッド表面調整剤とを含む。
かかる構成によると、ダミー研磨工程（ｂ）において研磨液中のパッド表面調整剤がコロイダルシリカのパッド表面への吸着を阻止する。これにより、研磨対象基板を研磨する工程（ｃ）においてもパッド表面は良好な状態に維持され、基板表面の微小うねりは低減する。
According to the present invention, a method for manufacturing a substrate is provided. This method includes a step (a) of pad-dressing a polishing pad; a step (b) of performing dummy polishing using the pad-dressed polishing pad and a polishing liquid; a step (c) of polishing a substrate to be polished; including. The polishing liquid contains colloidal silica abrasive grains and a pad surface conditioner.
According to such a configuration, the pad surface conditioner in the polishing liquid prevents the colloidal silica from adsorbing to the pad surface in the dummy polishing step (b). Thereby, even in the step (c) of polishing the substrate to be polished, the pad surface is maintained in a good state, and the micro waviness of the substrate surface is reduced.
ここに開示される技術の好ましい一態様では、前記工程（ｃ）において前記工程（ｂ）の研磨液を用いる。これにより、基板表面の微小うねりはさらに低減する。 In a preferred aspect of the technology disclosed herein, the polishing liquid of the step (b) is used in the step (c). Thereby, the fine waviness of the substrate surface is further reduced.
ここに開示される技術は、微小うねりの低減がより強く求められている磁気ディスク基板の製造方法に好ましく適用される。したがって、上記基板は磁気ディスク基板であることが好ましい。 The technology disclosed herein is preferably applied to a method of manufacturing a magnetic disk substrate that is more strongly required to reduce microwaviness. Therefore, the substrate is preferably a magnetic disk substrate.
また、この明細書によると、研磨用組成物が提供される。この研磨用組成物は、ここに開示される基板の製造方法において前記工程（ｂ）の研磨液として用いられる。また、この組成物は、コロイダルシリカ砥粒と、パッド表面調整剤と、を含む。この研磨用組成物を、ダミー研磨工程（ｂ）で使用することにより、研磨液中のパッド表面調整剤が、コロイダルシリカのパッド表面への吸着を阻止する。これにより、後の研磨工程においてパッド表面は良好な状態に維持され、基板表面の微小うねりは低減する。 Moreover, according to this specification, polishing composition is provided. This polishing composition is used as the polishing liquid in the step (b) in the substrate manufacturing method disclosed herein. Moreover, this composition contains colloidal silica abrasive grains and a pad surface conditioner. By using this polishing composition in the dummy polishing step (b), the pad surface conditioner in the polishing liquid prevents the colloidal silica from adsorbing to the pad surface. As a result, the pad surface is maintained in a good state in the subsequent polishing step, and micro-waviness on the substrate surface is reduced.
以下、本発明の好適な実施形態を説明する。なお、本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、当該分野における従来技術に基づく当業者の設計事項として把握され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。 Hereinafter, preferred embodiments of the present invention will be described. Note that matters other than matters specifically mentioned in the present specification and necessary for the implementation of the present invention can be grasped as design matters of those skilled in the art based on the prior art in this field. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.
＜基板の製造方法＞
ここに開示される技術は、基板を製造する方法を包含する。この製造方法は、研磨パッドをパッドドレッシングする工程（ａ）と；前記パッドドレッシングされた研磨パッドおよび研磨液を用いてダミー研磨する工程（ｂ）と；研磨対象基板を研磨する工程（ｃ）と；を含む。
<Substrate manufacturing method>
The technology disclosed herein includes a method of manufacturing a substrate. This manufacturing method includes a step (a) of pad-dressing a polishing pad; a step (b) of performing dummy polishing using the pad-dressed polishing pad and a polishing liquid; and a step (c) of polishing a substrate to be polished. ;including.
（基板）
ここに開示される研磨方法において、被研磨物となる基板は特に限定されない。例えば、磁気ディスク基板や、シリコンウエハ等の半導体基板のように、高精度な表面が要求される各種基板の製造に適用され得る。好ましい適用対象として、基材ディスクの表面にニッケルリンめっき層を有する磁気ディスク基板（Ｎｉ−Ｐ基板）が例示される。上記基材ディスクは、例えば、アルミニウム合金製、ガラス製等であり得る。このような基材ディスクの表面にニッケルリンめっき層以外の金属層または金属化合物層を備えたディスク基板であってもよい。なかでも好ましい適用対象として、アルミニウム合金製の基材ディスク上にニッケルリンめっき層を有するＮｉ−Ｐ基板が挙げられる。
(substrate)
In the polishing method disclosed herein, the substrate to be polished is not particularly limited. For example, the present invention can be applied to the production of various substrates that require a highly accurate surface such as a magnetic disk substrate and a semiconductor substrate such as a silicon wafer. As a preferable application object, a magnetic disk substrate (Ni-P substrate) having a nickel phosphorus plating layer on the surface of a base disk is exemplified. The base disk can be made of, for example, an aluminum alloy or glass. A disk substrate provided with a metal layer or metal compound layer other than the nickel phosphorus plating layer on the surface of such a base disk may be used. Among them, a preferable application target is a Ni-P substrate having a nickel phosphorus plating layer on a base disk made of aluminum alloy.
（研磨パッド）
ここに開示される方法に用いられる研磨パッドは、全体が発泡ポリウレタンにより構成されているパッド、発泡ポリウレタンの層が不織布等のパッド基材に支持されたパッド等のポリウレタン製研磨パッドであり得る。研磨パッドは、スウェードタイプのバフパッドであってもよいが、典型的には、表面をバフ加工していないノンバフ状態にある研磨パッド（いわゆるノンバフパッド）を用いることが好ましい。バフ加工とは、砥石等を利用し、表面を荒削りする処理であって、典型的には研磨パッドの表層部分を除去してポアの開口径や開口率を調整する処理のことをいう。発泡ポリウレタンとしては、例えば特開２００５−３３５０２８号公報に記載されているような、湿式成膜法で形成されたスウェードタイプと呼ばれるものが好ましく用いられる。
(Polishing pad)
The polishing pad used in the method disclosed herein may be a polyurethane polishing pad such as a pad composed entirely of foamed polyurethane or a pad in which a layer of foamed polyurethane is supported by a pad base material such as a nonwoven fabric. The polishing pad may be a suede-type buff pad, but it is typically preferable to use a polishing pad in a non-buffed state (so-called non-buff pad) whose surface is not buffed. Buffing is a process of roughing the surface using a grindstone or the like, and typically means a process of removing the surface layer portion of the polishing pad and adjusting the pore opening diameter and the aperture ratio. As the polyurethane foam, what is called a suede type formed by a wet film forming method as described in, for example, JP-A-2005-335028 is preferably used.
（工程（ａ））
工程（ａ）において、上記研磨パッドはパッドドレッシング処理される。この工程（ａ）は、典型的には、該研磨パッドが研磨装置に装着された状態で行われる。研磨装置としては、研磨パッドを用いる研磨の分野において公知の各種片面研磨装置、両面研磨装置等を用いることができ、特に限定されない。工程（ａ）は、このような研磨装置の定盤に研磨パッドが、例えば粘着テープや接着剤等を用いて固定された状態で好ましく実施され得る。
(Process (a))
In step (a), the polishing pad is subjected to pad dressing. This step (a) is typically performed with the polishing pad mounted on a polishing apparatus. As the polishing apparatus, various single-side polishing apparatuses, double-side polishing apparatuses and the like known in the field of polishing using a polishing pad can be used, and are not particularly limited. Step (a) can be preferably carried out in a state where the polishing pad is fixed to the surface plate of such a polishing apparatus using, for example, an adhesive tape or an adhesive.
パッドドレッシングは、公知の材料や条件を適用して行うことができる。好ましい一態様では、パッドドレッシングは、研磨装置の定盤に固定されている研磨パッドに対し、ステンレススチール等の金属からなる基材の表面に電着または焼結によりダイヤモンド粉末を固定させたパッドコンディショナー（パッドドレッサーとも呼ぶ。）を用いて、研磨パッドの表層を削りとる処理（典型的にはダイヤモンドドレッシング処理）であり得る。パッドコンディショナーとしては、例えば特開２００３−１１７８２３号公報に記載されているパッドコンディショナーが挙げられる。 The pad dressing can be performed by applying known materials and conditions. In a preferred embodiment, the pad dressing is a pad conditioner in which diamond powder is fixed to the surface of a substrate made of a metal such as stainless steel by electrodeposition or sintering with respect to the polishing pad fixed to the surface plate of the polishing apparatus. (Also referred to as a pad dresser) may be used to remove the surface layer of the polishing pad (typically, a diamond dressing treatment). An example of the pad conditioner is a pad conditioner described in Japanese Patent Application Laid-Open No. 2003-117823.
パッドドレッシングは、典型的には、上記研磨パッドの表層を、２μｍ以上削りとるか、あるいは研磨パッドの発泡部分（ポア）が２μｍ以上（通常は５μｍ以上４０μｍ以下）の平均開口径で表面に現れるまで削りとるように行われる。平均開口径が例えば４０μｍより大きいと、研磨パッドと基板との接触部分に圧力集中が起こりやすくなり、研磨基板表面の微小うねりが増大してしまう場合がある。
なお、研磨パッド表面の平均開口径は、走査電子顕微鏡（ＳＥＭ）写真の画像解析によって求められる。具体的には、写真１枚当たりポアが１０〜１５０個観察されるように倍率を調整し、５０個以上のポアの開口径を測定し、その平均値を採用すればよい。上記平均開口径は、例えば１５０μｍ×２５０μｍの区画内に存在するポアの平均開口径であり得る。
In pad dressing, the surface layer of the polishing pad is typically scraped by 2 μm or more, or the foamed portion (pore) of the polishing pad appears on the surface with an average opening diameter of 2 μm or more (usually 5 μm or more and 40 μm or less). It is done to scrape until. When the average opening diameter is larger than 40 μm, for example, pressure concentration is likely to occur at the contact portion between the polishing pad and the substrate, and the fine waviness on the surface of the polishing substrate may increase.
In addition, the average opening diameter of the polishing pad surface is calculated | required by the image analysis of a scanning electron microscope (SEM) photograph. Specifically, the magnification may be adjusted so that 10 to 150 pores can be observed per photograph, the opening diameters of 50 or more pores may be measured, and the average value may be adopted. The average opening diameter may be, for example, an average opening diameter of pores existing in a 150 μm × 250 μm section.
パッドドレッシングは、例えば１〜１．５Ｌ／分程度のレートで水を供給して行うとよい。水の供給量は、研磨パッド表面の単位面積（ｍ２）当たり３．５〜５．５Ｌ／分・ｍ２とすることが好ましい。パッドドレッシングの後、パッドの削り屑を除去するために、高圧ジェットまたはブラシドレス等で洗浄を行ってもよい。 The pad dressing may be performed by supplying water at a rate of about 1 to 1.5 L / min, for example. The supply amount of water is preferably 3.5 to 5.5 L / min · m 2 per unit area (m 2 ) of the polishing pad surface. After the pad dressing, cleaning may be performed with a high-pressure jet or a brush dress to remove pad shavings.
パッドドレッシングは、条件（ａ）：平均開口径（μｍ）×ポア数（個）／写真面積（μｍ２）≦０．４；を満たすように行うことが好ましい。上記条件（ａ）を満たさない場合、研磨パッドの表面状態よりも、パッド形状の影響を受けやすくなり、微小うねり低減効果が十分発揮されない場合がある。 The pad dressing is preferably performed so as to satisfy the condition (a): average opening diameter (μm) × number of pores (pieces) / photographic area (μm 2 ) ≦ 0.4. When the condition (a) is not satisfied, the pad shape is more easily affected than the surface state of the polishing pad, and the effect of reducing the fine waviness may not be sufficiently exhibited.
また、パッドドレッシングは、条件（ｂ）：ポア密度が３．０×１０−３（個／μｍ２）以上である；を満たすように行うことが好ましい。上記条件（ｂ）を満たさない場合、研磨パッドの表面状態よりも、パッド形状の影響を受けやすくなり、微小うねり低減効果が十分発揮されない場合がある。なお、ポア密度は、上述のＳＥＭ写真の画像解析によって求められる。特に好ましい一態様では、パッドドレッシングは、上記条件（ａ）および（ｂ）を満たすように行われる。 The pad dressing is preferably performed so as to satisfy the condition (b): the pore density is 3.0 × 10 −3 (pieces / μm 2 ) or more. When the condition (b) is not satisfied, the pad shape is more easily affected than the surface state of the polishing pad, and the effect of reducing the fine waviness may not be sufficiently exhibited. The pore density is obtained by image analysis of the above SEM photograph. In a particularly preferred embodiment, the pad dressing is performed so as to satisfy the above conditions (a) and (b).
なお、ここに開示される方法は、例えば、研磨パッドを研磨装置に装着する前に工程（ａ）を行い、その工程（ａ）を経た研磨パッドを研磨装置に装着して後述の工程（ｂ）を行う態様で実施することも可能である。 In the method disclosed herein, for example, the step (a) is performed before the polishing pad is mounted on the polishing apparatus, and the polishing pad that has undergone the step (a) is mounted on the polishing apparatus and the process (b) described later is performed. ) Is also possible.
（工程（ｂ））
上記工程（ａ）を行った後、パッドドレッシングされた研磨パッドおよび研磨液を用いてダミー研磨を行う（工程（ｂ））。具体的には、工程（ｂ）は、研磨装置にダミー基板をセットして、該研磨装置に研磨液を供給して、上記工程（ａ）を経た研磨パッドによりダミー基板を研磨する工程である。上記研磨は常法により行えばよい。例えば、工程（ａ）を経た研磨パッドが装着された研磨装置にダミー基板をセットし、該研磨装置の研磨パッドを通じて上記ダミー基板の表面（被研磨面）に研磨液を供給する。典型的には、上記研磨液を連続的に供給しつつ、ダミー基板の表面に研磨パッドを押しつけて両者を相対的に移動（例えば回転移動）させる。ダミー基板としては、被研磨物となる基板と同種のものを別途用意し、これをダミー基板として用いればよい。研磨液については後述する。研磨液の供給速度は特に限定されないが、ダミー基板１枚当たり毎分３〜１５ｍＬ供給されることが好ましい。
(Process (b))
After performing the step (a), dummy polishing is performed using a pad-dressed polishing pad and a polishing liquid (step (b)). Specifically, the step (b) is a step of setting a dummy substrate in a polishing apparatus, supplying a polishing liquid to the polishing apparatus, and polishing the dummy substrate with the polishing pad that has undergone the step (a). . The polishing may be performed by a conventional method. For example, a dummy substrate is set in a polishing apparatus equipped with the polishing pad that has undergone the step (a), and a polishing liquid is supplied to the surface (surface to be polished) of the dummy substrate through the polishing pad of the polishing apparatus. Typically, while supplying the polishing liquid continuously, the polishing pad is pressed against the surface of the dummy substrate to move both relatively (for example, rotational movement). As the dummy substrate, a substrate of the same type as the substrate to be polished may be separately prepared and used as the dummy substrate. The polishing liquid will be described later. The supply speed of the polishing liquid is not particularly limited, but it is preferable to supply 3 to 15 mL per minute per dummy substrate.
工程（ｂ）の時間は、特に限定されず、通常は所定の研磨レートが安定して得られるまで行われる。工程（ｂ）は少なくとも２０分以上（より好ましくは６０分以上）行うことが好ましい。ダミー研磨は通常、５分以上２０分以下程度の時間内で行われる研磨を５回以上（好ましくは１０回以上）繰り返す工程であり得る。ダミー 研磨時の温度は特に限定されないが、２０〜３５℃とすることが好ましい。 The time of the step (b) is not particularly limited, and is usually performed until a predetermined polishing rate is stably obtained. Step (b) is preferably carried out for at least 20 minutes or more (more preferably 60 minutes or more). The dummy polishing can be a step in which polishing performed usually within a time period of about 5 minutes to 20 minutes is repeated 5 times or more (preferably 10 times or more). The temperature at the time of dummy polishing is not particularly limited, but is preferably 20 to 35 ° C.
（工程（ｃ））
ここに開示される方法は、研磨対象基板を研磨する工程（ｃ）をさらに含む。具体的には、工程（ｂ）が終了すると、必要に応じて洗浄を行う等した後、ダミー基板を取り外し、研磨対象である基板を研磨装置にセットする。そして、研磨装置に研磨液を供給して、上記研磨パッドにより基板を研磨する。上記研磨は常法により行えばよい。例えば、上記研磨パッドが装着された研磨装置に研磨対象（被研磨物）としての基板をセットし、該研磨装置の研磨パッドを通じて上記被研磨物の表面（被研磨面）に研磨液を供給する。典型的には、上記研磨液を連続的に供給しつつ、被研磨物の表面に研磨パッドを押しつけて両者を相対的に移動（例えば回転移動）させる。かかる研磨工程を経て被研磨物の研磨が完了する。その後、必要に応じて洗浄、乾燥等を行うことで、基板は製造され得る。
(Process (c))
The method disclosed herein further includes a step (c) of polishing the substrate to be polished. Specifically, after step (b) is completed, after performing cleaning as necessary, the dummy substrate is removed, and the substrate to be polished is set in the polishing apparatus. Then, a polishing liquid is supplied to the polishing apparatus, and the substrate is polished by the polishing pad. The polishing may be performed by a conventional method. For example, a substrate as an object to be polished (object to be polished) is set in a polishing apparatus equipped with the polishing pad, and a polishing liquid is supplied to the surface (surface to be polished) of the object to be polished through the polishing pad of the polishing apparatus. . Typically, while supplying the polishing liquid continuously, the polishing pad is pressed against the surface of the object to be polished, and both are relatively moved (for example, rotated). The polishing of the object to be polished is completed through the polishing process. Then, a board | substrate can be manufactured by performing washing | cleaning, drying, etc. as needed.
工程（ｃ）に使用される研磨液としては、基板の研磨に使用され得る各種研磨液を使用すればよく特に制限はない。上記研磨液は、典型的には、少なくとも砥粒および水を含む。研磨装置に供給される研磨液は、当初の研磨用組成物に濃度調整（例えば希釈）やｐＨ調整等の操作を加えて調製された研磨液であり得る。あるいは、当初の研磨用組成物をそのまま研磨液として用いてもよい。工程（ｃ）に使用される研磨液として、工程（ｂ）の研磨液と異なる組成の研磨液を用いてもよいが、微小うねり低減の観点から、工程（ｃ）に使用される研磨液として、工程（ｂ）の研磨液と同種の研磨液を用いることが好ましい。 The polishing liquid used in the step (c) is not particularly limited as long as various polishing liquids that can be used for polishing the substrate are used. The polishing liquid typically contains at least abrasive grains and water. The polishing liquid supplied to the polishing apparatus may be a polishing liquid prepared by adding operations such as concentration adjustment (for example, dilution) and pH adjustment to the initial polishing composition. Alternatively, the initial polishing composition may be used as a polishing liquid as it is. As the polishing liquid used in the step (c), a polishing liquid having a composition different from that of the polishing liquid in the step (b) may be used. From the viewpoint of reducing microwaviness, the polishing liquid used in the step (c) It is preferable to use the same type of polishing liquid as used in the step (b).
＜研磨用組成物＞
次に、工程（ｂ）に使用される研磨液（以下、研磨用組成物ともいう。）について説明する。この研磨液は、好ましくはさらに工程（ｃ）に使用されるものであり得る。
<Polishing composition>
Next, the polishing liquid (hereinafter also referred to as a polishing composition) used in the step (b) will be described. This polishing liquid may preferably be further used in step (c).
ここに開示される技術において使用される研磨用組成物は、コロイダルシリカ砥粒と、パッド表面調整剤と、を含む。この研磨液はまた、典型的には水を含む。水としては、イオン交換水（脱イオン水）、蒸留水、純水等を用いることができる。 The polishing composition used in the technology disclosed herein includes colloidal silica abrasive grains and a pad surface conditioner. This polishing liquid also typically contains water. As water, ion exchange water (deionized water), distilled water, pure water, or the like can be used.
（砥粒）
ここに開示される研磨用組成物は、コロイダルシリカ砥粒の１種または２種以上を含む。コロイダルシリカ砥粒の平均一次粒子径は、典型的には５ｎｍ以上、好ましくは１０ｎｍ以上である。平均一次粒子径の増大によって、より高い研磨レートが実現され得る。上記砥粒の平均一次粒子径の上限は特に限定されない。より平滑性の高い表面を得る観点から、平均一次粒子径は、典型的には３００ｎｍ以下、好ましくは１００ｎｍ以下、より好ましくは６０ｎｍ以下、さらに好ましくは３０ｎｍ以下である。例えば、一次研磨を終えたＮｉ−Ｐ基板を研磨する用途向けの研磨用組成物において、上記の平均一次粒子径を有する砥粒を好ましく採用し得る。小径のコロイダルシリカ砥粒はよりパッド表面に堆積しやすいと考えられることから、小径（例えば平均一次粒子径３０ｎｍ以下）のコロイダルシリカ砥粒を含む態様において、後述のパッド表面調整剤を使用することの効果はよりよく発揮され得る。
(Abrasive grains)
The polishing composition disclosed herein contains one or more colloidal silica abrasive grains. The average primary particle diameter of the colloidal silica abrasive is typically 5 nm or more, preferably 10 nm or more. By increasing the average primary particle size, a higher polishing rate can be realized. The upper limit of the average primary particle diameter of the abrasive grains is not particularly limited. From the viewpoint of obtaining a more smooth surface, the average primary particle size is typically 300 nm or less, preferably 100 nm or less, more preferably 60 nm or less, and even more preferably 30 nm or less. For example, in a polishing composition intended for polishing a Ni-P substrate that has been subjected to primary polishing, abrasive grains having the above average primary particle diameter can be preferably employed. Since it is considered that small-diameter colloidal silica abrasive particles are more likely to be deposited on the pad surface, a pad surface conditioner described below should be used in an embodiment including small-diameter (for example, average primary particle diameter of 30 nm or less) colloidal silica abrasive grains. The effect of can be better exhibited.
なお、砥粒の平均一次粒子径は、例えば、ＢＥＴ法により測定される比表面積Ｓ（ｍ２／ｇ）から平均一次粒子径（ｎｍ）＝２７２７／Ｓの式により算出することができる。砥粒の比表面積の測定は、例えば、マイクロメリテックス社製の表面積測定装置、商品名「Ｆｌｏｗ Ｓｏｒｂ ＩＩ ２３００」を用いて行うことができる。 In addition, the average primary particle diameter of an abrasive grain can be calculated by the formula of average primary particle diameter (nm) = 2727 / S from the specific surface area S (m 2 / g) measured by the BET method, for example. The measurement of the specific surface area of the abrasive grains can be performed using, for example, a surface area measuring device manufactured by Micromeritex Co., Ltd., trade name “Flow Sorb II 2300”.
研磨用組成物中におけるコロイダルシリカ砥粒の平均二次粒子径は、典型的には１０ｎｍ以上であり、通常は２０ｎｍ超、好ましくは３０ｎｍ超、より好ましくは４０ｎｍ超、さらに好ましくは５０ｎｍ超である。平均二次粒子径の増大によって、より高い研磨レートが実現され得る。上記砥粒の平均二次粒子径の上限は特に限定されず、例えば１μｍ以下であり得る。分散安定性等の観点から、平均二次粒子径は、通常は５００ｎｍ以下が適当であり、好ましくは２００ｎｍ以下、より好ましくは１５０ｎｍ以下、さらに好ましくは１１０ｎｍ以下、特に好ましくは７０ｎｍ以下である。さらに高品位の表面を得る観点から、平均二次粒子径は、例えば５５ｎｍ以下であってもよい。 The average secondary particle size of the colloidal silica abrasive grains in the polishing composition is typically 10 nm or more, usually more than 20 nm, preferably more than 30 nm, more preferably more than 40 nm, still more preferably more than 50 nm. . By increasing the average secondary particle size, a higher polishing rate can be realized. The upper limit of the average secondary particle diameter of the abrasive grains is not particularly limited, and may be, for example, 1 μm or less. From the viewpoint of dispersion stability and the like, the average secondary particle size is usually suitably 500 nm or less, preferably 200 nm or less, more preferably 150 nm or less, still more preferably 110 nm or less, and particularly preferably 70 nm or less. Further, from the viewpoint of obtaining a high quality surface, the average secondary particle diameter may be, for example, 55 nm or less.
この明細書において、砥粒の平均二次粒子径とは、超音波方式で測定される粒度分布における体積基準の平均粒子径（mean particle diameter）をいう。平均二次粒子径は、例えば、日本ルフト社製の超音波方式粒度分布・ゼータ電位測定装置（商品名「ＤＴ−１２００」）を用いて測定することができる。 In this specification, the average secondary particle diameter of abrasive grains refers to a volume-based mean particle diameter in a particle size distribution measured by an ultrasonic method. The average secondary particle diameter can be measured using, for example, an ultrasonic particle size distribution / zeta potential measuring apparatus (trade name “DT-1200”) manufactured by Nippon Luft.
研磨用組成物中におけるコロイダルシリカ砥粒の含有量（すなわちコロイダルシリカ砥粒の濃度）は、特に制限されない。上記コロイダルシリカ砥粒の濃度は、例えば３０重量％以下とすることができ、通常は２０重量％以下が好ましく、１５重量％以下がより好ましく、１０重量％以下がさらに好ましい。また、上記砥粒の濃度は、１重量％以上であることが好ましく、より好ましくは３重量％以上である。砥粒濃度が低すぎると、物理的な研磨作用が小さくなり、研磨速度が低下するため、実用上好ましくない場合がある。上記砥粒濃度は、被研磨物に供給される研磨液の砥粒濃度にも好ましく適用され得る。 The content of colloidal silica abrasive grains in the polishing composition (that is, the concentration of colloidal silica abrasive grains) is not particularly limited. The concentration of the colloidal silica abrasive grains can be, for example, 30% by weight or less, usually 20% by weight or less, more preferably 15% by weight or less, and still more preferably 10% by weight or less. The concentration of the abrasive grains is preferably 1% by weight or more, more preferably 3% by weight or more. If the abrasive concentration is too low, the physical polishing action becomes small and the polishing rate decreases, which may be undesirable in practice. The abrasive concentration can be preferably applied to the abrasive concentration of the polishing liquid supplied to the object to be polished.
なお、ここに開示される研磨用組成物は、本発明の効果を損なわない範囲内で、コロイダルシリカ砥粒以外の砥粒を含有してもよい。コロイダルシリカ砥粒以外の砥粒としては、例えばヒュームドシリカ砥粒、沈降性シリカ砥粒等のシリカ砥粒や、アルミナ砥粒、チタニア砥粒、ジルコニア砥粒、セリア砥粒等の金属酸化物砥粒、ポリアクリル酸等の樹脂砥粒等の非シリカ砥粒の１種または２種以上を使用することができる。これらコロイダルシリカ砥粒以外の砥粒の含有量は、コロイダルシリカ砥粒の含有量の１００重量％（すなわち同量）未満であることが適当であり、好ましくは５０重量％以下（例えば３０重量％以下、典型的には１０重量％以下）である。ここに開示される技術は、コロイダルシリカ砥粒以外の砥粒を実質的に含まない態様で実施することができる。 In addition, the polishing composition disclosed here may contain abrasive grains other than colloidal silica abrasive grains as long as the effects of the present invention are not impaired. Examples of abrasive grains other than colloidal silica abrasive grains include silica abrasive grains such as fumed silica abrasive grains and precipitated silica abrasive grains, and metal oxides such as alumina abrasive grains, titania abrasive grains, zirconia abrasive grains, and ceria abrasive grains. One type or two or more types of non-silica abrasive grains such as abrasive grains and resin abrasive grains such as polyacrylic acid can be used. The content of abrasive grains other than these colloidal silica abrasive grains is suitably less than 100% by weight (that is, the same amount) of the content of colloidal silica abrasive grains, preferably 50% by weight or less (for example, 30% by weight). Hereinafter, typically 10 wt% or less). The technique disclosed here can be implemented in an aspect that does not substantially contain abrasive grains other than colloidal silica abrasive grains.
（パッド表面調整剤）
ここに開示される研磨用組成物は、パッド表面調整剤を含むことによって特徴づけられる。研磨用組成物がパッド表面調整剤を含むことによって、基板の微小うねりは低減される。その理由を明らかにする必要はないが、例えば次のことが推察される。パッドドレッシング後の研磨パッドの表面は、平坦に削りとられることによって、気泡が開口してできたポアが多数存在し、毛羽立った部分（ナップ）も存在している状態となっている。このような表面状態の研磨パッドに対しダミー研磨を行うことで、毛羽立った部分（ナップ）は除去され、上記表面状態は整えられる。これにより、研磨パッド表面は、基板表面を均一にかつ好適なレートで研磨するうえで好ましい状態となり、微小うねりを低減するうえでも望ましい状態になると考えられる。上記のような表面状態を表面全体において均一に維持しながらパッド表面が摩耗し除去されていけば、微小うねりの低減は理想的に実現され得ると考えられる。しかし、コロイダルシリカ砥粒を用いる態様では、コロイダルシリカが研磨中にパッド表面に吸着して、シリカコーティングともいうべき硬質薄膜となり、これがパッド表面を微細なレベルで不均一な状態にしていることが判明した。より具体的には、通常であれば研磨において除去されていくべき部分が上記硬質被膜で覆われるために均一に除去されずポアを覆うように残存していると推察される。実際に、コロイダルシリカ砥粒を用いた従来の研磨後のパッド表面では、ポア開口の減少が認められており、上記推察を支持している。ここに開示されるパッド表面調整剤は、コロイダルシリカの吸着を阻止するようにパッド表面の状態を良好に調整するものである。具体的には、パッドドレッシングに続くダミー研磨工程において、コロイダルシリカのパッド表面への吸着を阻止し、シリカコーティングの発生を抑制することで、パッド表面の微細な不均一化を防止し、微小うねり低減の実現に寄与する。
(Pad surface conditioner)
The polishing composition disclosed herein is characterized by including a pad surface conditioner. When the polishing composition contains a pad surface conditioner, the microwaviness of the substrate is reduced. Although it is not necessary to clarify the reason, for example, the following is presumed. The surface of the polishing pad after the pad dressing is scraped flat, so that there are a large number of pores formed by opening bubbles, and there are also fuzzy portions (nap). By performing dummy polishing on the polishing pad in such a surface state, the fuzzy portion (nap) is removed and the surface state is adjusted. Thereby, it is considered that the surface of the polishing pad is in a preferable state for polishing the substrate surface uniformly and at a suitable rate, and is in a preferable state for reducing microwaviness. If the pad surface is worn and removed while maintaining the surface state as described above uniformly over the entire surface, it is considered that the reduction of microwaviness can be realized ideally. However, in the embodiment using colloidal silica abrasive grains, the colloidal silica is adsorbed on the pad surface during polishing to form a hard thin film that can also be referred to as silica coating, which makes the pad surface non-uniform at a fine level. found. More specifically, it is presumed that a portion that should be removed in polishing is covered with the hard film, and is not removed uniformly and remains to cover the pores. Actually, on the pad surface after the conventional polishing using colloidal silica abrasive grains, a decrease in pore opening is recognized, which supports the above inference. The pad surface conditioner disclosed herein adjusts the state of the pad surface well so as to prevent the adsorption of colloidal silica. Specifically, in the dummy polishing process following the pad dressing, the colloidal silica is prevented from adsorbing to the pad surface, and the generation of silica coating is suppressed, thereby preventing the fine unevenness of the pad surface and the micro waviness. Contributes to the realization of reduction.
パッド表面調整剤としては、研磨液中において上記の機能を発揮し得るものであればよく、その限りにおいて特に制限はない。パッド表面調整剤としては、例えばスルホン酸系化合物等の有機化合物から選択され得る。なお、ここでいうスルホン酸系化合物の概念には、スルホン酸系化合物およびその塩が包含される。具体的には、ナフタレンスルホン酸ホルムアルデヒド縮合物、メチルナフタレンスルホン酸ホルムアルデヒド縮合物、アントラセンスルホン酸ホルムアルデヒド縮合物、ベンゼンスルホン酸ホルムアルデヒド縮合物等のポリアルキルアリールスルホン酸系化合物；メラミンスルホン酸ホルムアルデヒド縮合物等のメラミンホルマリン樹脂スルホン酸系化合物；リグニンスルホン酸、変成リグニンスルホン酸等のリグニンスルホン酸系化合物；アミノアリールスルホン酸−フェノール−ホルムアルデヒド縮合物等の芳香族アミノスルホン酸系化合物；その他、ポリイソプレンスルホン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリイソアミレンスルホン酸等のスルホン酸系化合物、その塩（例えばナトリウム塩、カリウム塩等のアルカリ金属塩）等から選択され得る。なかでも、ナフタレンスルホン酸ホルムアルデヒド縮合物、メチルナフタレンスルホン酸ホルムアルデヒド縮合物等のナフタレンスルホン酸系化合物およびその塩が好ましく、ナフタレンスルホン酸ホルムアルデヒド縮合物ナトリウム塩がより好ましい。 The pad surface conditioner is not particularly limited as long as it can exhibit the above function in the polishing liquid. The pad surface conditioner can be selected from organic compounds such as sulfonic acid compounds. The concept of the sulfonic acid compound here includes a sulfonic acid compound and a salt thereof. Specifically, polyalkylaryl sulfonic acid compounds such as naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate, benzene sulfonic acid formaldehyde condensate; melamine sulfonic acid formaldehyde condensate, etc. Melamine formalin resin sulfonic acid compounds; lignin sulfonic acid compounds such as lignin sulfonic acid and modified lignin sulfonic acid; aromatic amino sulfonic acid compounds such as aminoaryl sulfonic acid-phenol-formaldehyde condensates; and other polyisoprene sulfones Sulfonic acid compounds such as acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyisoamylene sulfonic acid, and salts thereof (for example, sodium salts, potassium salts, etc.) It may be selected from Li metal salt) and the like. Of these, naphthalene sulfonic acid-based compounds such as naphthalene sulfonic acid formaldehyde condensate and methyl naphthalene sulfonic acid formaldehyde condensate and salts thereof are preferable, and naphthalene sulfonic acid formaldehyde condensate sodium salt is more preferable.
パッド表面調整剤の分子量は特に限定されないが、コロイダルシリカのパッド表面への吸着を十分に阻止する観点から、凡そ４００以上（例えば１０００以上、典型的には１５００以上）であることが好ましく、３０万以下であることが適当であり、好ましくは５万以下（例えば９０００以下、典型的には５０００以下）である。なお、この明細書において分子量とは、構造式から求められる分子量または重量平均分子量（標準ポリスチレン基準）を指す。 The molecular weight of the pad surface modifier is not particularly limited, but is preferably about 400 or more (for example, 1000 or more, typically 1500 or more) from the viewpoint of sufficiently preventing the colloidal silica from adsorbing to the pad surface. It is suitable that it is 10,000 or less, preferably 50,000 or less (for example, 9000 or less, typically 5000 or less). In this specification, the molecular weight refers to a molecular weight or a weight average molecular weight (standard polystyrene standard) determined from a structural formula.
パッド表面調整剤の含有量は、コロイダルシリカのパッド表面への吸着を十分に阻止する観点から、０．００１重量％以上とすることが適当であり、好ましくは０．００５重量％以上、より好ましくは０．０１重量％以上、さらに好ましくは０．０２重量％以上である。また、上記と同様の理由から、上記含有量は１０重量％以下とすることが適当であり、好ましくは５重量％以下、例えば１重量％以下である。 The content of the pad surface modifier is suitably 0.001% by weight or more, preferably 0.005% by weight or more, more preferably from the viewpoint of sufficiently preventing the adsorption of colloidal silica to the pad surface. Is 0.01% by weight or more, more preferably 0.02% by weight or more. For the same reason as described above, the content is suitably 10% by weight or less, preferably 5% by weight or less, for example 1% by weight or less.
（分散剤）
研磨用組成物は、分散安定性向上等の目的で、水溶性ポリマー（典型的にはアニオン性水溶性ポリマー）等の分散剤を含んでもよい。分散剤としては、例えばポリスチレンスルホン酸およびその塩等が挙げられる。上記ポリスチレンスルホン酸系化合物の塩としては、ナトリウム塩、カリウム塩等のアルカリ金属塩が好ましい。分散剤の他の例として、ポリアクリル酸およびその塩（例えば、ナトリウム塩等のアルカリ金属塩）等が挙げられる。分散剤を使用することで、パッド表面調整剤の効果がよりよく発揮され得る。
(Dispersant)
The polishing composition may contain a dispersant such as a water-soluble polymer (typically an anionic water-soluble polymer) for the purpose of improving dispersion stability. Examples of the dispersant include polystyrene sulfonic acid and a salt thereof. The salt of the polystyrene sulfonic acid compound is preferably an alkali metal salt such as sodium salt or potassium salt. Other examples of the dispersant include polyacrylic acid and a salt thereof (for example, an alkali metal salt such as a sodium salt). By using the dispersant, the effect of the pad surface conditioner can be more effectively exhibited.
上記水溶性ポリマーの分子量は、分散安定性向上効果を十分に発揮する観点から、凡そ１万以上（例えば５万超）であることが適当である。上記分子量の上限は特に限定されないが、凡そ８０万以下（例えば６０万以下、典型的には３０万以下）程度であり得る。 The molecular weight of the water-soluble polymer is suitably about 10,000 or more (for example, more than 50,000) from the viewpoint of sufficiently exhibiting the dispersion stability improving effect. The upper limit of the molecular weight is not particularly limited, but may be about 800,000 or less (for example, 600,000 or less, typically 300,000 or less).
分散剤を含む態様の研磨用組成物では、分散剤の含有量を、例えば０．００１重量％以上とすることが適当である。上記含有量は、研磨後の表面の平滑性等の観点から、好ましくは０．００５重量％以上、より好ましくは０．０１重量％以上、さらに好ましくは０．０２重量％以上である。また、上記含有量は通常、１０重量％以下とすることが適当であり、好ましくは５重量％以下、例えば１重量％以下である。 In the polishing composition containing the dispersant, it is appropriate that the content of the dispersant is, for example, 0.001% by weight or more. The content is preferably 0.005% by weight or more, more preferably 0.01% by weight or more, and further preferably 0.02% by weight or more from the viewpoint of the smoothness of the surface after polishing. In addition, the content is usually suitably 10% by weight or less, preferably 5% by weight or less, for example 1% by weight or less.
（アニオン性界面活性剤）
ここに開示される研磨用組成物は、アニオン性界面活性剤を含んでもよい。上記アニオン性界面活性剤は、典型的には分散剤と比べて比較的低分子量の化合物である。アニオン性界面活性剤の具体例としては、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸アンモニウム、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム等が挙げられる。
(Anionic surfactant)
The polishing composition disclosed herein may contain an anionic surfactant. The anionic surfactant is typically a compound having a relatively low molecular weight as compared with a dispersant. Specific examples of the anionic surfactant include sodium lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate and the like.
アニオン性界面活性剤を含む態様の研磨用組成物では、アニオン性界面活性剤の含有量を、例えば０．００１重量％以上とすることが適当である。上記含有量は、研磨後の表面の平滑性等の観点から、好ましくは０．００５重量％以上、より好ましくは０．０１重量％以上、さらに好ましくは０．０２重量％以上である。また、上記含有量は通常、１０重量％以下とすることが適当であり、好ましくは５重量％以下、例えば１重量％以下である。 In the polishing composition containing the anionic surfactant, it is appropriate that the content of the anionic surfactant is, for example, 0.001% by weight or more. The content is preferably 0.005% by weight or more, more preferably 0.01% by weight or more, and further preferably 0.02% by weight or more from the viewpoint of the smoothness of the surface after polishing. In addition, the content is usually suitably 10% by weight or less, preferably 5% by weight or less, for example 1% by weight or less.
（酸または塩）
研磨用組成物は、砥粒および水の他に、研磨促進剤として、酸または塩を含有することが好ましい。ここで、酸または塩を含むとは、酸および塩の少なくとも一方を含むことを指し、酸を含み塩を含まない態様、塩を含み酸を含まない態様、および酸と塩の両方を含む態様、のいずれをも包含する意味である。
(Acid or salt)
In addition to the abrasive grains and water, the polishing composition preferably contains an acid or salt as a polishing accelerator. Here, including an acid or a salt refers to including at least one of an acid and a salt, an embodiment including an acid and no salt, an embodiment including a salt and no acid, and an embodiment including both an acid and a salt It is the meaning which includes any of these.
酸の例としては、無機酸や有機酸（例えば、炭素原子数が１〜１０程度の有機カルボン酸、有機ホスホン酸、有機スルホン酸等）が挙げられるが、これらに限定されない。酸は、１種を単独でまたは２種以上を組み合わせて用いることができる。
無機酸の具体例としては、硝酸、硫酸、塩酸、リン酸、次亜リン酸、ホスホン酸、ホウ酸等が挙げられる。
有機酸の具体例としては、クエン酸、マレイン酸、リンゴ酸、グリコール酸、コハク酸、イタコン酸、マロン酸、イミノ二酢酸、グルコン酸、乳酸、マンデル酸、酒石酸、クロトン酸、ニコチン酸、酢酸、アジピン酸、ギ酸、シュウ酸、プロピオン酸、吉草酸、カプロン酸、カプリル酸、カプリン酸、シクロヘキサンカルボン酸、フェニル酢酸、安息香酸、クロトン酸、メタクリル酸、グルタル酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸、グリコール酸、タルトロン酸、グリセリン酸、ヒドロキシ酪酸、ヒドロキシ酢酸、ヒドロキシ安息香酸、サリチル酸、イソクエン酸、メチレンコハク酸、没食子酸、アスコルビン酸、ニトロ酢酸、オキサロ酢酸、グリシン、アラニン、グルタミン酸、アスパラギン酸、ニコチン酸、ピコリン酸、メチルアシッドホスフェート、エチルアシッドホスフェート、エチルグリコールアシッドホスフェート、イソプロピルアシッドホスフェート、フィチン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、アミノトリ（メチレンホスホン酸）、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、エタン−１，１−ジホスホン酸、エタン−１，１，２−トリホスホン酸、エタン−１−ヒドロキシ−１，１−ジホスホン酸、エタンヒドロキシ−１，１，２−トリホスホン酸、エタン−１，２−ジカルボキシ−１，２−ジホスホン酸、メタンヒドロキシホスホン酸、２−ホスホノブタン−１，２−ジカルボン酸、１−ホスホノブタン−２，３，４−トリカルボン酸、α−メチルホスホノコハク酸、アミノポリ（メチレンホスホン酸）、メタンスルホン酸、エタンスルホン酸、アミノエタンスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、２−ナフタレンスルホン酸等が挙げられる。
Examples of the acid include, but are not limited to, inorganic acids and organic acids (for example, organic carboxylic acids having 1 to 10 carbon atoms, organic phosphonic acids, organic sulfonic acids, etc.). An acid can be used individually by 1 type or in combination of 2 or more types.
Specific examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, hypophosphorous acid, phosphonic acid, boric acid and the like.
Specific examples of organic acids include citric acid, maleic acid, malic acid, glycolic acid, succinic acid, itaconic acid, malonic acid, iminodiacetic acid, gluconic acid, lactic acid, mandelic acid, tartaric acid, crotonic acid, nicotinic acid, acetic acid , Adipic acid, formic acid, oxalic acid, propionic acid, valeric acid, caproic acid, caprylic acid, capric acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, crotonic acid, methacrylic acid, glutaric acid, fumaric acid, phthalic acid, isophthalic acid Acid, terephthalic acid, glycolic acid, tartronic acid, glyceric acid, hydroxybutyric acid, hydroxyacetic acid, hydroxybenzoic acid, salicylic acid, isocitric acid, methylene succinic acid, gallic acid, ascorbic acid, nitroacetic acid, oxaloacetic acid, glycine, alanine, glutamic acid , Aspartic acid, nicotinic acid, picoline , Methyl acid phosphate, ethyl acid phosphate, ethyl glycol acid phosphate, isopropyl acid phosphate, phytic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (Methylenephosphonic acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid Ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphono Examples include succinic acid, aminopoly (methylenephosphonic acid), methanesulfonic acid, ethanesulfonic acid, aminoethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and 2-naphthalenesulfonic acid.
塩の例としては、上述した無機酸または有機酸の金属塩、例えばリチウム塩、ナトリウム塩、カリウム塩等のアルカリ金属塩；上述した無機酸または有機酸のアンモニウム塩、例えばテトラメチルアンモニウム塩、テトラエチルアンモニウム塩等の第四級アンモニウム塩；上述した無機酸または有機酸のアルカノールアミン塩、例えばモノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩；等が挙げられる。
上述した無機酸または有機酸の金属塩の具体例としては、リン酸三カリウム、リン酸水素二カリウム、リン酸二水素カリウム、リン酸三ナトリウム、リン酸水素二ナトリウム、リン酸二水素ナトリウム等のアルカリ金属リン酸塩およびアルカリ金属リン酸水素塩；等が挙げられる。
その他、塩の例としては、グルタミン酸二酢酸のアルカリ金属塩（例えばリチウム塩、ナトリウム塩、カリウム塩等。以下同じ。）、ジエチレントリアミン五酢酸のアルカリ金属塩、ヒドロキシエチルエチレンジアミン三酢酸のアルカリ金属塩、トリエチレンテトラミン六酢酸のアルカリ金属塩；等が挙げられる。例えば、Ｌ−グルタミン酸二酢酸四ナトリウムを好ましく使用し得る。塩は、１種を単独でまたは２種以上を組み合わせて用いることができる。
Examples of the salt include the above-described inorganic or organic acid metal salts, for example, alkali metal salts such as lithium salt, sodium salt, potassium salt; the above-mentioned inorganic or organic acid ammonium salts, such as tetramethylammonium salt, tetraethyl Quaternary ammonium salts such as ammonium salts; alkanolamine salts of the above-mentioned inorganic or organic acids such as monoethanolamine salts, diethanolamine salts, triethanolamine salts; and the like.
Specific examples of the inorganic acid or organic acid metal salt described above include tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, and the like. Alkali metal phosphates and alkali metal hydrogen phosphates; and the like.
Other examples of salts include alkali metal salts of glutamic acid diacetic acid (for example, lithium salt, sodium salt, potassium salt, etc.), alkali metal salt of diethylenetriaminepentaacetic acid, alkali metal salt of hydroxyethylethylenediaminetriacetic acid, An alkali metal salt of triethylenetetramine hexaacetic acid; For example, tetrasodium L-glutamate diacetate can be preferably used. A salt can be used individually by 1 type or in combination of 2 or more types.
ここに開示される技術は、リン酸を有する酸または塩を含む研磨液を用いる態様で好ましく実施され得る。パッド表面調整剤は、リン酸を介したコロイダルシリカの凝集を抑制し、パッド表面へのコロイダルシリカの吸着を好適に阻止し得る。なお、ここに開示される技術は、硫酸、有機ホスホン酸（例えば１−ヒドロキシエチリデン−１，１−ジホスホン酸）の少なくとも１種（例えば両方）を実質的に含まない態様でも好ましく実施することができる。 The technique disclosed here can be preferably implemented in an embodiment using a polishing liquid containing an acid or salt having phosphoric acid. The pad surface conditioner can suppress aggregation of colloidal silica via phosphoric acid and can suitably prevent the adsorption of colloidal silica to the pad surface. In addition, the technique disclosed here can be preferably implemented even in an embodiment that does not substantially contain at least one (for example, both) of sulfuric acid and organic phosphonic acid (for example, 1-hydroxyethylidene-1,1-diphosphonic acid). it can.
このような酸または塩は、典型的には後述する酸化剤と合わせて用いられることにより、研磨促進剤として効果的に作用し得る。研磨効率の観点から好ましい酸として、メタンスルホン酸、硫酸、硝酸、リン酸、フィチン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸等が例示される。なかでも好ましい酸として、メタンスルホン酸、クエン酸およびリン酸が挙げられる。研磨効率の観点から好ましい塩として、リン酸塩やリン酸水素塩、グルタミン酸二酢酸のアルカリ金属塩、ジエチレントリアミン五酢酸のアルカリ金属塩、ヒドロキシエチルエチレンジアミン三酢酸のアルカリ金属塩、トリエチレンテトラミン六酢酸のアルカリ金属塩等が挙げられる。 Such an acid or salt can typically act effectively as a polishing accelerator when used in combination with an oxidizing agent described later. Preferred acids from the viewpoint of polishing efficiency include methanesulfonic acid, sulfuric acid, nitric acid, phosphoric acid, phytic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and the like. Of these, methanesulfonic acid, citric acid, and phosphoric acid are preferable acids. Preferred salts from the viewpoint of polishing efficiency include phosphates and hydrogen phosphates, alkali metal salts of glutamic acid diacetic acid, alkali metal salts of diethylenetriaminepentaacetic acid, alkali metal salts of hydroxyethylethylenediaminetriacetic acid, and triethylenetetraminehexaacetic acid. Examples include alkali metal salts.
研磨用組成物中に酸または塩を含む場合、その含有量は、０．１重量％以上であることが好ましく、より好ましくは０．５重量％以上である。酸または塩の含有量が少なすぎると、研磨速度が低下し、実用上好ましくない場合がある。また、研磨用組成物中に酸または塩を含む場合、その含有量は、１０重量％以下であることが好ましく、より好ましくは５重量％以下である。酸または塩の含有量が多すぎると、研磨対象物の表面精度が悪くなり、実用上好ましくない場合がある。 When the polishing composition contains an acid or a salt, the content is preferably 0.1% by weight or more, more preferably 0.5% by weight or more. If the acid or salt content is too small, the polishing rate decreases, which may be undesirable in practice. Further, when the polishing composition contains an acid or salt, the content is preferably 10% by weight or less, more preferably 5% by weight or less. If the acid or salt content is too high, the surface accuracy of the object to be polished is deteriorated, which may be undesirable in practice.
（酸化剤）
ここに開示される研磨用組成物は、砥粒および水の他に、研磨促進剤として、酸化剤を含有することが好ましい。酸化剤の例としては、過酸化物、硝酸またはその塩、ペルオキソ酸またはその塩、過マンガン酸またはその塩、クロム酸またはその塩、酸素酸またはその塩、金属塩類、硫酸類等が挙げられるが、これらに限定されない。酸化剤は、１種を単独でまたは２種以上を組み合わせて用いることができる。酸化剤の具体例としては、過酸化水素、過酸化ナトリウム、過酸化バリウム、硝酸、硝酸鉄、硝酸アルミニウム、硝酸アンモニウム、ペルオキソ二硫酸、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸金属塩、ペルオキソリン酸、ペルオキソ硫酸、ペルオキソホウ酸ナトリウム、過ギ酸、過酢酸、過安息香酸、過フタル酸、次亜臭素酸、次亜ヨウ素酸、塩素酸、臭素酸、ヨウ素酸、過ヨウ素酸、過塩素酸、次亜塩素酸、次亜塩素酸ナトリウム、次亜塩素酸カルシウム、過マンガン酸カリウム、クロム酸金属塩、重クロム酸金属塩、塩化鉄、硫酸鉄、クエン酸鉄、硫酸アンモニウム鉄等が挙げられる。好ましい酸化剤として、過酸化水素、硝酸鉄、ペルオキソ二硫酸および硝酸が例示される。少なくとも過酸化水素を含むことが好ましく、過酸化水素からなることがより好ましい。
(Oxidant)
The polishing composition disclosed herein preferably contains an oxidizing agent as a polishing accelerator in addition to the abrasive grains and water. Examples of the oxidizing agent include peroxide, nitric acid or a salt thereof, peroxo acid or a salt thereof, permanganic acid or a salt thereof, chromic acid or a salt thereof, oxygen acid or a salt thereof, metal salt, sulfuric acid, and the like. However, it is not limited to these. An oxidizing agent can be used individually by 1 type or in combination of 2 or more types. Specific examples of the oxidizing agent include hydrogen peroxide, sodium peroxide, barium peroxide, nitric acid, iron nitrate, aluminum nitrate, ammonium nitrate, peroxodisulfuric acid, ammonium peroxodisulfate, peroxodisulfate metal salt, peroxophosphoric acid, peroxosulfuric acid. , Sodium peroxoborate, performic acid, peracetic acid, perbenzoic acid, perphthalic acid, hypobromite, hypoiodous acid, chloric acid, bromic acid, iodic acid, periodic acid, perchloric acid, hypochlorous acid Examples thereof include acid, sodium hypochlorite, calcium hypochlorite, potassium permanganate, metal chromate, metal dichromate, iron chloride, iron sulfate, iron citrate, and iron iron sulfate. Preferable oxidizing agents include hydrogen peroxide, iron nitrate, peroxodisulfuric acid and nitric acid. It preferably contains at least hydrogen peroxide, and more preferably consists of hydrogen peroxide.
研磨用組成物中に酸化剤を含む場合、その含有量は、０．１重量％以上であることが好ましく、より好ましくは０．３重量％以上である。酸化剤の含有量が少なすぎると、研磨対象物を酸化する速度が遅くなり、研磨速度が低下するため、実用上好ましくない場合がある。また、研磨用組成物中に酸化剤を含む場合、その含有量は、３重量％以下であることが好ましく、より好ましくは１．５重量％以下である。酸化剤の含有量が多すぎると、研磨対象物の表面精度が悪くなったり、コストの点等から実用上好ましくない場合がある。 When the polishing composition contains an oxidizing agent, the content is preferably 0.1% by weight or more, and more preferably 0.3% by weight or more. If the content of the oxidizing agent is too small, the rate of oxidizing the object to be polished becomes slow and the polishing rate is lowered, which may be undesirable in practice. Moreover, when an oxidizing agent is included in polishing composition, it is preferable that the content is 3 weight% or less, More preferably, it is 1.5 weight% or less. When there is too much content of an oxidizing agent, the surface precision of a grinding | polishing target object may worsen, or it may not be practically preferable from the point of cost.
（塩基性化合物）
研磨用組成物には、塩基性化合物を含有させることができる。ここで塩基性化合物とは、研磨用組成物に添加されることによって該組成物のｐＨを上昇させる機能を有する化合物を指す。例えば、アルカリ金属の水酸化物、第四級アンモニウムまたはその塩、アンモニア、アミン、リン酸塩やリン酸水素塩、有機酸塩等が挙げられる。塩基性化合物は、１種を単独でまたは２種以上を組み合わせて用いることができる。
(Basic compound)
The polishing composition can contain a basic compound. Here, the basic compound refers to a compound having a function of increasing the pH of the composition when added to the polishing composition. Examples thereof include alkali metal hydroxides, quaternary ammonium or salts thereof, ammonia, amines, phosphates, hydrogen phosphates, and organic acid salts. A basic compound can be used individually by 1 type or in combination of 2 or more types.
アルカリ金属の水酸化物の具体例としては、水酸化カリウム、水酸化ナトリウム等が挙げられる。
第四級アンモニウムまたはその塩の具体例としては、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウム等の水酸化第四級アンモニウムが挙げられる。
アミンの具体例としては、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、エチレンジアミン、モノエタノールアミン、Ｎ−（β−アミノエチル）エタノールアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、無水ピペラジン、ピペラジン六水和物、１−（２−アミノエチル）ピペラジン、Ｎ−メチルピペラジン、グアニジン、イミダゾールやトリアゾール等のアゾール類、等が挙げられる。
リン酸塩やリン酸水素塩の具体例としては、リン酸三カリウム、リン酸水素二カリウム、リン酸二水素カリウム、リン酸三ナトリウム、リン酸水素二ナトリウム、リン酸二水素ナトリウム等のアルカリ金属塩、リン酸アンモニウム、リン酸水素二アンモニウム、リン酸二水素アンモニウム等のアンモニウム塩が挙げられる。
Specific examples of the alkali metal hydroxide include potassium hydroxide and sodium hydroxide.
Specific examples of the quaternary ammonium or a salt thereof include quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide.
Specific examples of amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N- (β-aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, anhydrous piperazine , Piperazine hexahydrate, 1- (2-aminoethyl) piperazine, N-methylpiperazine, guanidine, azoles such as imidazole and triazole, and the like.
Specific examples of phosphates and hydrogen phosphates include alkalis such as tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, trisodium phosphate, disodium hydrogen phosphate, and sodium dihydrogen phosphate. Examples thereof include metal salts, ammonium salts such as ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate.
（イオン強度）
特に限定するものではないが、好ましい一態様に係る研磨用組成物は、砥粒含有量が６重量％となる濃度におけるイオン強度が０．１５０ｍｏｌ／Ｌ以下であり得る。イオン強度が０．１５０ｍｏｌ／Ｌ以下である研磨用組成物は、コロイダルシリカの分散安定性に優れる傾向がある。かかる観点から、イオン強度が０．１１０ｍｏｌ／Ｌ未満である研磨用組成物がさらに好ましい。イオン強度の下限は特に限定されず、研磨用組成物を所望のｐＨに調整できればよい。研磨速度の向上の観点から、通常は、イオン強度が０．０１ｍｏｌ／Ｌ以上であることが好ましく、０．０２ｍｏｌ／Ｌ以上であることがより好ましく、０．０３ｍｏｌ／Ｌ以上であることがさらに好ましい。
(Ionic strength)
Although not particularly limited, the polishing composition according to a preferred embodiment may have an ionic strength of 0.150 mol / L or less at a concentration at which the abrasive grain content is 6% by weight. A polishing composition having an ionic strength of 0.150 mol / L or less tends to be excellent in the dispersion stability of colloidal silica. From this viewpoint, a polishing composition having an ionic strength of less than 0.110 mol / L is more preferable. The lower limit of the ionic strength is not particularly limited as long as the polishing composition can be adjusted to a desired pH. From the viewpoint of improving the polishing rate, usually, the ionic strength is preferably 0.01 mol / L or more, more preferably 0.02 mol / L or more, and further preferably 0.03 mol / L or more. preferable.
本明細書中においてイオン強度とは、研磨用組成物の砥粒含有量が６重量％となる濃度において、該研磨用組成物中の全てのイオンについて下記式（１）により算出される値をいう。目的とする研磨用組成物の砥粒含有量が６重量％とは異なる場合には、水の量を増減することにより砥粒含有量６重量％に濃度調整した場合における研磨用組成物についてイオン強度を算出する。 In this specification, the ionic strength is a value calculated by the following formula (1) for all ions in the polishing composition at a concentration at which the abrasive grain content of the polishing composition is 6% by weight. Say. When the abrasive content of the target polishing composition is different from 6% by weight, the ion for the polishing composition when the concentration is adjusted to 6% by weight by increasing or decreasing the amount of water. Calculate the intensity.
ここで、式（１）中のＩは、イオン強度［ｍｏｌ／Ｌ］を表す。ｍｉは、各イオンのモル濃度［ｍｏｌ／Ｌ］を表す。ｚｉは、各イオンの電荷（価数）を表す。各イオンのモル濃度は、イオン強度の算出に係る研磨用組成物のｐＨ域において解離する（イオン化する）各物質のイオン量（割合）から算出される。例えば、砥粒含有量６重量％に調製された研磨用組成物中に１ｍｏｌ／Ｌの濃度で含まれる物質Ａが、そのｐＨ域において５０％しかイオン化しない場合、イオン強度に反映させるモル濃度は０．５ｍｏｌ／Ｌとなる。 Here, I in Formula (1) represents ionic strength [mol / L]. m i represents a molar concentration [mol / L] of each ion. z i represents the charge (valence) of each ion. The molar concentration of each ion is calculated from the ion amount (ratio) of each substance dissociated (ionized) in the pH range of the polishing composition relating to the calculation of ionic strength. For example, when the substance A contained at a concentration of 1 mol / L in the polishing composition prepared to an abrasive content of 6% by weight ionizes only 50% in the pH range, the molar concentration reflected in the ionic strength is 0.5 mol / L.
イオン強度の算出に係る研磨用組成物（すなわち、砥粒含有量が６重量％となるように必要に応じて濃度調整を行った研磨用組成物）のｐＨ域で解離している各物質のイオン量（割合）は、各物質の解離定数（電離定数、酸解離定数）によって求めることができる。
例えば、研磨用組成物中でＡ−とＨ＋に解離する物質ＡＨの酸解離定数がｐＫａであり、上記物質ＡＨが研磨用組成物中に１．０ｍｏｌ／Ｌ含まれており、その研磨用組成物のｐＨが３である場合には、Ａ−の濃度ｍＡは、（１０−ｐＫａ×１．０［ｍｏｌ／Ｌ］）／１．０×１０−３の式で求められる。
研磨用組成物に塩を添加する場合には、その塩のカウンターイオンのモル濃度によってイオン強度を算出する。例えば、研磨用組成物中でＡ−とＢ＋に解離する物質ＡＢについては、研磨用組成物中ＡＨまたはＢＯＨについては、分けてイオン強度を算出する。
また、研磨用組成物中で一段階以上の多段階の解離をする物質を含む研磨用組成物においては、それぞれの段階で解離しているイオンについてイオン強度を求める。
なお、イオン強度の算出は、研磨用組成物の温度が２５℃である場合について行うものとする。
Each of the substances dissociated in the pH range of the polishing composition related to the calculation of the ionic strength (that is, the polishing composition whose concentration is adjusted as necessary so that the abrasive content is 6% by weight). The ion amount (ratio) can be determined from the dissociation constants (ionization constant, acid dissociation constant) of each substance.
For example, the acid dissociation constant of a substance AH that dissociates into A − and H + in the polishing composition is pKa, and the substance AH is contained in the polishing composition at 1.0 mol / L. When the pH of the composition is 3, the concentration A of A − can be obtained by the formula (10 −pKa × 1.0 [mol / L]) / 1.0 × 10 −3 .
When a salt is added to the polishing composition, the ionic strength is calculated from the molar concentration of the counter ion of the salt. For example, for the substance AB that dissociates into A − and B + in the polishing composition, the ionic strength is calculated separately for AH or BOH in the polishing composition.
In the polishing composition containing a substance that dissociates in one or more stages in the polishing composition, the ionic strength is determined for ions dissociated in each stage.
In addition, calculation of ionic strength shall be performed when the temperature of polishing composition is 25 degreeC.
研磨用組成物のイオン強度は、例えば、該組成物に含まれるイオン性化合物の種類および使用量（濃度）により調節することができる。上記イオン性化合物としては、上述した研磨促進剤や塩基性化合物として機能する化合物を利用し得る。これら以外のイオン性化合物を用いてイオン強度を調節してもよい。 The ionic strength of the polishing composition can be adjusted by, for example, the type and amount (concentration) of the ionic compound contained in the composition. As the ionic compound, the above-described polishing accelerator or a compound that functions as a basic compound can be used. The ionic strength may be adjusted using ionic compounds other than these.
（その他の成分）
研磨用組成物は、本発明の効果が著しく妨げられない範囲で、キレート剤や防腐剤等の、研磨用組成物（典型的には、Ｎｉ−Ｐ基板等のような磁気ディスク基板の研磨に用いられる研磨用組成物）に用いられ得る公知の添加剤を、必要に応じてさらに含有してもよい。
(Other ingredients)
The polishing composition is used for polishing a polishing composition (typically, a magnetic disk substrate such as a Ni-P substrate) such as a chelating agent or a preservative as long as the effects of the present invention are not significantly hindered. You may further contain the well-known additive which may be used for the polishing composition used as needed.
キレート剤の例としては、アミノカルボン酸系キレート剤および有機ホスホン酸系キレート剤が挙げられる。アミノカルボン酸系キレート剤の例には、エチレンジアミン四酢酸、エチレンジアミン四酢酸ナトリウム、ニトリロ三酢酸、ニトリロ三酢酸ナトリウム、ニトリロ三酢酸アンモニウム、ヒドロキシエチルエチレンジアミン三酢酸、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム、ジエチレントリアミン五酢酸、ジエチレントリアミン五酢酸ナトリウム、トリエチレンテトラミン六酢酸およびトリエチレンテトラミン六酢酸ナトリウムが含まれる。有機ホスホン酸系キレート剤の例には、２−アミノエチルホスホン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、アミノトリ（メチレンホスホン酸）、エチレンジアミンテトラキス（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、エタン−１，１−ジホスホン酸、エタン−１，１，２−トリホスホン酸、エタン−１−ヒドロキシ−１，１−ジホスホン酸、エタン−１−ヒドロキシ−１，１，２−トリホスホン酸、エタン−１，２−ジカルボキシ−１，２−ジホスホン酸、メタンヒドロキシホスホン酸、２−ホスホノブタン−１，２−ジカルボン酸、１−ホスホノブタン−２，３，４−トリカルボン酸およびα−メチルホスホノコハク酸が含まれる。これらのうち有機ホスホン酸系キレート剤がより好ましく、なかでも好ましいものとしてエチレンジアミンテトラキス（メチレンホスホン酸）およびジエチレントリアミンペンタ（メチレンホスホン酸）が挙げられる。特に好ましいキレート剤として、エチレンジアミンテトラキス（メチレンホスホン酸）が挙げられる。 Examples of chelating agents include aminocarboxylic acid chelating agents and organic phosphonic acid chelating agents. Examples of aminocarboxylic acid chelating agents include ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid sodium, nitrilotriacetic acid, nitrilotriacetic acid sodium, nitrilotriacetic acid ammonium, hydroxyethylethylenediaminetriacetic acid, hydroxyethylethylenediamine sodium triacetate, diethylenetriaminepentaacetic acid Diethylenetriamine sodium pentaacetate, triethylenetetramine hexaacetic acid and sodium triethylenetetramine hexaacetate. Examples of organic phosphonic acid chelating agents include 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic). Acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid Ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphospho Nosuccinic acid is included. Of these, organic phosphonic acid-based chelating agents are more preferable, and ethylenediaminetetrakis (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid) are particularly preferable. A particularly preferred chelating agent is ethylenediaminetetrakis (methylenephosphonic acid).
上述のような研磨用組成物は、典型的には該研磨用組成物を含む研磨液の形態で被研磨物（例えば磁気ディスク基板）に供給されて、該被研磨物の研磨に用いられる。上記研磨液は、例えば、研磨用組成物を希釈して調製されたものであり得る。あるいは、研磨用組成物をそのまま研磨液として使用してもよい。すなわち、ここに開示される技術における研磨用組成物の概念には、被研磨物に供給される研磨液（ワーキングスラリー）と、希釈して研磨液として用いられる濃縮液との双方が包含される。 The polishing composition as described above is typically supplied to an object to be polished (for example, a magnetic disk substrate) in the form of a polishing liquid containing the polishing composition and used for polishing the object to be polished. The polishing liquid may be prepared, for example, by diluting a polishing composition. Or you may use polishing composition as polishing liquid as it is. That is, the concept of the polishing composition in the technique disclosed herein includes both a polishing liquid (working slurry) supplied to the object to be polished and a concentrated liquid that is diluted and used as the polishing liquid. .
研磨用組成物は、被研磨物に供給される前には濃縮された形態（濃縮液の形態）であってもよい。かかる濃縮液の形態の研磨用組成物は、製造、流通、保存等の際における利便性やコスト低減等の観点から有利である。濃縮倍率は、例えば１．５倍〜５０倍程度とすることができる。濃縮液の貯蔵安定性等の観点から、通常は、２倍〜２０倍（典型的には２倍〜１０倍）程度の濃縮倍率が適当である。
このように濃縮液の形態にある研磨用組成物は、所望のタイミングで希釈して研磨液を調製し、その研磨液を被研磨物に供給する態様で好適に使用することができる。
The polishing composition may be in a concentrated form (concentrated liquid form) before being supplied to the object to be polished. Such a polishing composition in the form of a concentrated solution is advantageous from the viewpoints of convenience, cost reduction, etc. during production, distribution, storage and the like. The concentration factor can be set to about 1.5 to 50 times, for example. From the viewpoint of the storage stability of the concentrate, a concentration factor of about 2 to 20 times (typically 2 to 10 times) is usually appropriate.
Thus, the polishing composition in the form of a concentrated liquid can be suitably used in such a manner that a polishing liquid is prepared by diluting at a desired timing and the polishing liquid is supplied to an object to be polished.
研磨用組成物のｐＨは特に限定されない。例えば、研磨レートや表面平滑性等の観点から、ｐＨ４以下が好ましく、ｐＨ３以下がより好ましい。研磨液において上記ｐＨが実現されるように、必要に応じて有機酸、無機酸等のｐＨ調整剤を含有させることができる。上記ｐＨは、例えば、Ｎｉ−Ｐの研磨に用いられる研磨液に好ましく適用され得る。 The pH of the polishing composition is not particularly limited. For example, from the viewpoint of polishing rate, surface smoothness, etc., pH 4 or less is preferable, and pH 3 or less is more preferable. If necessary, a pH adjusting agent such as an organic acid or an inorganic acid can be contained so that the above pH is realized in the polishing liquid. The pH can be preferably applied to, for example, a polishing liquid used for polishing Ni—P.
以下、本発明に関するいくつかの実施例を説明するが、本発明をかかる実施例に示すものに限定することを意図したものではない。なお、以下の説明において「部」および「％」は、特に断りがない限り重量基準である。 Several examples relating to the present invention will be described below, but the present invention is not intended to be limited to those shown in the examples. In the following description, “parts” and “%” are based on weight unless otherwise specified.
＜実施例および比較例＞
（研磨液の調製）
砥粒、パッド表面調整剤、酸または塩、塩基性化合物、３１％過酸化水素水およびイオン交換水を混合して、表１に示す組成および性質を有する研磨液１〜８を調製した。酸または塩、塩基性化合物の使用量は、研磨液のイオン強度を見ながら適宜調整した。表１中、「−」は不使用を意味する。また、ＧＬＤＡ４ＮａはＬ−グルタミン酸二酢酸四ナトリウムの略称である。
<Examples and Comparative Examples>
(Preparation of polishing liquid)
Abrasive grains, pad surface conditioner, acid or salt, basic compound, 31% hydrogen peroxide water and ion-exchanged water were mixed to prepare polishing liquids 1 to 8 having the compositions and properties shown in Table 1. The amount of acid, salt, or basic compound used was appropriately adjusted while observing the ionic strength of the polishing liquid. In Table 1, “-” means non-use. GLDA4Na is an abbreviation for L-glutamic acid diacetate tetrasodium.
（パッドドレッシング）
研磨パッドとして、ポリウレタン製でスウェードタイプのノンバフパッドを用意した。上記研磨パッドのサイズは、外径６４０ｍｍ、内径２３２ｍｍのドーナツ盤状であり、したがって研磨面の面積は２７９２ｃｍ２である。上記研磨パッド２枚を、両面研磨装置（スピードファム社製「９Ｂ−５Ｐ」）の上定盤と下定盤に各１枚ずつ固定した。ダイヤモンドドレッサーを２枚／キャリア×５キャリア（計１０枚）装填し、１〜１．５Ｌ／分のレートでイオン交換水を供給しながら、研磨パッドの研磨面に対してパッドドレッシングを行った。
(Pad dressing)
As a polishing pad, a polyurethane-made suede-type non-buff pad was prepared. The size of the polishing pad is a donut shape having an outer diameter of 640 mm and an inner diameter of 232 mm. Therefore, the area of the polishing surface is 2792 cm 2 . The two polishing pads were each fixed to the upper and lower surface plates of a double-side polishing apparatus (“9B-5P” manufactured by Speed Fam Co., Ltd.). Two diamond dressers / carriers × 5 carriers (10 in total) were loaded, and pad dressing was performed on the polishing surface of the polishing pad while supplying ion-exchanged water at a rate of 1 to 1.5 L / min.
（ダミー研磨）
次いで、上記研磨パッドが引き続き定盤に固定された状態で、該研磨パッドの研磨面に高圧ジェット水流を吹き付けて洗浄した。そして、上記両面研磨装置にダミー基板をセットし、表２に示す研磨液を用いて下記の条件でダミー研磨を行った。
ダミー基板としては、表面に無電解ニッケルリンめっき層を備えた直径３．５インチ（約９５ｍｍ）、厚さ１．２７ｍｍのハードディスク用アルミニウム基板を用いた。
［ダミー研磨条件］
研磨荷重：１２０ｇ／ｃｍ２
基板装填枚数：２枚／キャリア×４キャリア（計８枚）
下定盤回転数：６０ｒｐｍ
研磨液の供給レート：８３ｍＬ／分
研磨時間：５分
研磨回数：１２回
(Dummy polishing)
Next, in the state where the polishing pad was continuously fixed to the surface plate, the polishing surface of the polishing pad was washed with a high-pressure jet water stream. Then, a dummy substrate was set in the double-side polishing apparatus, and dummy polishing was performed using the polishing liquid shown in Table 2 under the following conditions.
As the dummy substrate, an aluminum substrate for a hard disk having a diameter of 3.5 inches (about 95 mm) and a thickness of 1.27 mm and having an electroless nickel phosphorus plating layer on the surface thereof was used.
[Dummy polishing conditions]
Polishing load: 120 g / cm 2
Number of substrates loaded: 2 / carrier x 4 carriers (8 total)
Lower platen rotation speed: 60rpm
Polishing liquid supply rate: 83 mL / min Polishing time: 5 minutes Number of polishing times: 12 times
（研磨対象基板の研磨：本研磨）
ダミー研磨終了後、ダミー基板を取り外し、研磨対象基板をセットした。研磨対象基板としては、表面に無電解ニッケルリンめっき層を備えた直径３．５インチ（約９５ｍｍ）、厚さ１．２７ｍｍのハードディスク用アルミニウム基板を、Ｓｃｈｍｉｔｔ Ｍｅａｓｕｒｅｍｅｎｔ Ｓｙｓｔｅｍ社製レーザースキャン式表面粗さ計「ＴＭＳ−３０００ＷＲＣ」により測定される表面粗さ（算術平均粗さ（Ｒａ））の値が６Åとなるように予備研磨したものを使用した。表２に示す研磨液を用いて下記の条件で研磨対象基板を研磨した。
［研磨条件］
研磨荷重：１２０ｇ／ｃｍ２
基板装填枚数：２枚／キャリア×４キャリア（計８枚）
下定盤回転数：６０ｒｐｍ
研磨液の供給レート：８３ｍＬ／分
研磨時間：５分
(Polishing the substrate to be polished: main polishing)
After completion of dummy polishing, the dummy substrate was removed and the substrate to be polished was set. As a substrate to be polished, a hard disk aluminum substrate having a diameter of 3.5 inches (about 95 mm) and a thickness of 1.27 mm provided with an electroless nickel phosphorus plating layer on its surface, a laser scanning surface roughness manufactured by Schmitt Measurement System. What was pre-polished so that the value of the surface roughness (arithmetic mean roughness (Ra)) measured by the total “TMS-3000WRC” was 6 mm was used. The substrate to be polished was polished using the polishing liquid shown in Table 2 under the following conditions.
[Polishing conditions]
Polishing load: 120 g / cm 2
Number of substrates loaded: 2 / carrier x 4 carriers (8 total)
Lower platen rotation speed: 60rpm
Polishing liquid supply rate: 83 mL / min Polishing time: 5 minutes
＜評価＞
［毛羽立ち］
パッドドレッシングを終えた後の研磨パッド表面およびダミー研磨を終えた後の研磨パッド表面について、ＳＥＭで観察を行い、以下の２水準で評価した。結果を表２に示す。
〇：パッドドレッシング後に存在していたパッド表面の毛羽立ちが、ダミー研磨後には除去されていた。
×：パッドドレッシング後に存在していたパッド表面の毛羽立ちが、ダミー研磨後にも除去されていなかった。
<Evaluation>
[Fuzzing]
The polishing pad surface after the pad dressing and the polishing pad surface after the dummy polishing were observed by SEM and evaluated according to the following two levels. The results are shown in Table 2.
◯: The fuzz on the pad surface that existed after the pad dressing was removed after the dummy polishing.
X: The fuzz on the pad surface that existed after the pad dressing was not removed even after the dummy polishing.
［ポア開口率］
研磨対象基板の研磨を終えた後の研磨パッド表面につき、ＳＥＭで観察を行い、以下の２水準で評価した。結果を表２に示す。
〇：パッド表面に十分数のポアが認められた。すなわち気泡が十分に開口していた。
×：パッド表面のポアが塞がれており、開口状態は十分でなく、表面がコロイダルシリカによって覆われていた。
[Pore opening ratio]
The surface of the polishing pad after polishing the substrate to be polished was observed with an SEM and evaluated according to the following two levels. The results are shown in Table 2.
A: A sufficient number of pores were observed on the pad surface. That is, the bubbles were sufficiently open.
X: The pores on the pad surface were blocked, the opening state was not sufficient, and the surface was covered with colloidal silica.
［微小うねり］
各実施例および各比較例に係る基板（研磨後の研磨対象基板）２枚の表裏、計４面につき、非接触表面形状測定機（商品名「ＮｅｗＶｉｅｗ」、Ｚｙｇｏ社製）を用いて、レンズ倍率２．５倍、ズーム倍率０．５倍、バンドパスフィルターを８０〜５００μｍの条件で微小うねりを測定した。研磨後の基板の中心から径方向外側に３７ｍｍの位置に対し、９０°ずつ４ヵ所を測定し、その平均値を微小うねり値（Å）として求めた。結果を表２に示す。
[Slight swell]
Using the non-contact surface shape measuring instrument (trade name “NewView”, manufactured by Zygo) for the front and back surfaces of the two substrates (substrates to be polished after polishing) according to each example and each comparative example, a total of four surfaces, lenses Micro waviness was measured under the conditions of a magnification of 2.5 times, a zoom magnification of 0.5 times, and a band pass filter of 80 to 500 μm. With respect to a position 37 mm radially outward from the center of the substrate after polishing, four positions were measured in 90 ° increments, and the average value was determined as a fine waviness value (Å). The results are shown in Table 2.
表２に示されるように、ダミー研磨工程で用いるダミー研磨用組成物として、コロイダルシリカ砥粒を含む研磨液にパッド表面調整剤を含ませたものを用いた実施例１〜５では、パッド表面は十分に開口し、基板表面の微小うねりを有意に低減することができた。一方、ダミー研磨工程で用いるダミー研磨用組成物として、パッド表面調整剤を含まない研磨液を用いた比較例１〜４、パッド表面調整剤の機能を持たない分散剤を含む研磨液を用いた比較例５、６では、パッド表面の毛羽立ちは除去されず、パッド表面は十分に開口せず、実施例１〜５と比べて微小うねりは高い値を示した。これらの結果から、コロイダルシリカ砥粒を含む研磨液にパッド表面調整剤を含ませた研磨液を、ダミー研磨工程で用いるダミー研磨用組成物として用いることで、微小うねりを低減し得ることがわかる。 As shown in Table 2, in Examples 1 to 5 in which the pad polishing agent containing a colloidal silica abrasive was used as a dummy polishing composition used in the dummy polishing step, the pad surface was used. Was sufficiently open, and micro-waviness on the substrate surface could be significantly reduced. On the other hand, as a dummy polishing composition used in the dummy polishing step, Comparative Examples 1 to 4 using a polishing liquid not containing a pad surface conditioner, a polishing liquid containing a dispersant having no function of a pad surface conditioner was used. In Comparative Examples 5 and 6, the fuzz on the pad surface was not removed, the pad surface was not sufficiently opened, and the microwaviness was higher than in Examples 1-5. From these results, it can be seen that by using a polishing liquid containing a pad surface conditioner in a polishing liquid containing colloidal silica abrasive grains as a dummy polishing composition used in a dummy polishing step, microwaviness can be reduced. .
以上、本発明の具体例を詳細に説明したが、これらは例示にすぎず、特許請求の範囲を限定するものではない。特許請求の範囲に記載の技術には、以上に例示した具体例を様々に変形、変更したものが含まれる。 Specific examples of the present invention have been described in detail above, but these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.
Claims (4)
前記パッドドレッシングされた研磨パッドおよび研磨液を用いてダミー研磨する工程（ｂ）と；
研磨対象基板を研磨する工程（ｃ）と；
を含み、
前記研磨液は、コロイダルシリカ砥粒とパッド表面調整剤とを含む、基板の製造方法。 Step (a) of pad dressing the polishing pad;
Performing a dummy polishing using the pad-dressed polishing pad and a polishing liquid (b);
A step (c) of polishing the substrate to be polished;
Including
The said polishing liquid is a manufacturing method of a board | substrate containing colloidal silica abrasive and a pad surface conditioner.
コロイダルシリカ砥粒と、パッド表面調整剤と、を含む、研磨用組成物。 A polishing composition used as a polishing liquid in the step (b) in the production method according to any one of claims 1 to 3,
A polishing composition comprising a colloidal silica abrasive and a pad surface conditioner.
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| JP6616795B2 (en) * | 2016-04-22 | 2019-12-04 | 日揮触媒化成株式会社 | Polishing abrasive dispersion containing silica composite fine particles |
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