JP2020037669A - Polishing composition and polishing system - Google Patents
Polishing composition and polishing system Download PDFInfo
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- JP2020037669A JP2020037669A JP2019010484A JP2019010484A JP2020037669A JP 2020037669 A JP2020037669 A JP 2020037669A JP 2019010484 A JP2019010484 A JP 2019010484A JP 2019010484 A JP2019010484 A JP 2019010484A JP 2020037669 A JP2020037669 A JP 2020037669A
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- JP
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- Prior art keywords
- polishing
- polishing composition
- acid
- less
- polished
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 256
- 239000000203 mixture Substances 0.000 title claims abstract description 112
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000006061 abrasive grain Substances 0.000 claims abstract description 51
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000002612 dispersion medium Substances 0.000 claims abstract description 14
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 125000004434 sulfur atom Chemical group 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000008119 colloidal silica Substances 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- -1 silica Chemical class 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 239000011164 primary particle Substances 0.000 description 9
- 239000011163 secondary particle Substances 0.000 description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
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- 239000000377 silicon dioxide Substances 0.000 description 8
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- 239000003002 pH adjusting agent Substances 0.000 description 7
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- 239000002253 acid Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
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- 125000002091 cationic group Chemical group 0.000 description 5
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- 239000000654 additive Substances 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 2
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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- LVYLCBNXHHHPSB-UHFFFAOYSA-N 2-hydroxyethyl salicylate Chemical compound OCCOC(=O)C1=CC=CC=C1O LVYLCBNXHHHPSB-UHFFFAOYSA-N 0.000 description 2
- QHQNYHZHLAAHRW-UHFFFAOYSA-N 2-trimethoxysilylethanamine Chemical compound CO[Si](OC)(OC)CCN QHQNYHZHLAAHRW-UHFFFAOYSA-N 0.000 description 2
- AULKDLUOQCUNOK-UHFFFAOYSA-N 3,5-dichloro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC(Cl)=C(O)C(Cl)=C1 AULKDLUOQCUNOK-UHFFFAOYSA-N 0.000 description 2
- QGNLHMKIGMZKJX-UHFFFAOYSA-N 3-chloro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(Cl)=C1 QGNLHMKIGMZKJX-UHFFFAOYSA-N 0.000 description 2
- IHCCAYCGZOLTEU-UHFFFAOYSA-N 3-furoic acid Chemical compound OC(=O)C=1C=COC=1 IHCCAYCGZOLTEU-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 description 2
- AMUTYVGRCVFCCD-UHFFFAOYSA-N 5,6-diaminopyridine-3-carboxylic acid Chemical compound NC1=CC(C(O)=O)=CN=C1N AMUTYVGRCVFCCD-UHFFFAOYSA-N 0.000 description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- GCSPRLPXTPMSTL-IBDNADADSA-N [(2s,3r,4s,5s,6r)-2-[(2s,3s,4s,5r)-3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[C@@]1([C@]2(CO)[C@H]([C@H](O)[C@@H](CO)O2)O)O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O GCSPRLPXTPMSTL-IBDNADADSA-N 0.000 description 2
- ZPVGIKNDGJGLCO-VGAMQAOUSA-N [(2s,3r,4s,5s,6r)-2-[(2s,3s,4s,5r)-3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)O[C@@]1([C@]2(CO)[C@H]([C@H](O)[C@@H](CO)O2)O)O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O ZPVGIKNDGJGLCO-VGAMQAOUSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- 238000002296 dynamic light scattering Methods 0.000 description 2
- VFPFQHQNJCMNBZ-UHFFFAOYSA-N ethyl gallate Chemical compound CCOC(=O)C1=CC(O)=C(O)C(O)=C1 VFPFQHQNJCMNBZ-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
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- 239000004745 nonwoven fabric Substances 0.000 description 2
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
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- 239000004814 polyurethane Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
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- 239000005720 sucrose Substances 0.000 description 2
- UHUFTBALEZWWIH-UHFFFAOYSA-N tetradecanal Chemical compound CCCCCCCCCCCCCC=O UHUFTBALEZWWIH-UHFFFAOYSA-N 0.000 description 2
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- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、研磨用組成物および研磨システムに関する。 The present invention relates to a polishing composition and a polishing system.
近年、半導体基板表面の多層配線化に伴い、デバイスを製造する際に、半導体基板を研磨して平坦化する、いわゆる、化学的機械的研磨（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ；ＣＭＰ）技術が利用されている。ＣＭＰは、シリカやアルミナ、セリア等の砥粒、防食剤、界面活性剤などを含む研磨用組成物（スラリー）を用いて、半導体基板等の研磨対象物（被研磨物）の表面を平坦化する方法であり、研磨対象物（被研磨物）は、シリコン、ポリシリコン、シリコン酸化膜（酸化ケイ素）、シリコン窒化物や、金属等からなる配線、プラグなどである。 2. Description of the Related Art In recent years, as the surface of a semiconductor substrate has been multi-layered, a so-called chemical mechanical polishing (CMP) technique for polishing and flattening the semiconductor substrate when manufacturing a device has been used. CMP uses a polishing composition (slurry) containing abrasive grains such as silica, alumina, and ceria, an anticorrosive, a surfactant, and the like to planarize the surface of an object to be polished (an object to be polished) such as a semiconductor substrate. The object to be polished (substrate to be polished) is silicon, polysilicon, a silicon oxide film (silicon oxide), a silicon nitride, a wiring made of metal or the like, a plug, or the like.
たとえば、特許文献１では、半導体集積回路の平坦化工程において化学的機械的研磨に用いられる研磨液であって、四級アンモニウムカチオン、有機酸、無機粒子、ならびに一般式（Ｉ）で示される化合物および一般式（Ｉ）で示される構造単位を含む高分子の少なくとも一方を含み、ｐＨが１〜７の範囲であることを特徴とする研磨液が開示されている。また、特許文献２では、式（１）で表されるポリグリセリン誘導体（Ａ）、研磨材（Ｂ）、および水を含有する化学的機械的研磨用研磨組成物が開示されている。 For example, Patent Literature 1 discloses a polishing liquid used for chemical mechanical polishing in a step of planarizing a semiconductor integrated circuit, which comprises a quaternary ammonium cation, an organic acid, inorganic particles, and a compound represented by the general formula (I). Also disclosed is a polishing liquid containing at least one of the polymers containing the structural unit represented by the general formula (I), and having a pH in the range of 1 to 7. Patent Document 2 discloses a polishing composition for chemical mechanical polishing containing a polyglycerin derivative (A) represented by the formula (1), an abrasive (B), and water.
上記特許文献１および２に記載の研磨液によれば、酸化ケイ素膜の表面に発生するスクラッチを抑制することができるとしている。しかしながら、本発明者らの検討によれば、特許文献１および特許文献２に記載の技術では、スクラッチの抑制が未だ不十分であるという問題があることがわかった。 According to the polishing liquids described in Patent Documents 1 and 2, scratches generated on the surface of the silicon oxide film can be suppressed. However, according to the study of the present inventors, it has been found that the techniques described in Patent Documents 1 and 2 have a problem that the suppression of scratches is still insufficient.
したがって、本発明は、酸化ケイ素膜を含む研磨対象物の高い研磨速度を維持しつつ、酸化ケイ素膜を含む研磨対象物表面のスクラッチを十分に低減することができる研磨用組成物を提供することを目的とする。 Accordingly, the present invention provides a polishing composition that can sufficiently reduce scratches on the surface of a polishing target including a silicon oxide film while maintaining a high polishing rate of the polishing target including a silicon oxide film. With the goal.
上記の課題を解決すべく、本発明者らは鋭意研究を積み重ねた。その結果、酸化ケイ素膜を含む研磨対象物を研磨するために用いられる研磨用組成物であって、砥粒と、分配係数の対数値（ＬｏｇＰ）が１．０以上である化合物と、分散媒と、を含有し、ｐＨが７未満である、研磨用組成物により、上記課題が解決することを見出し、本発明を完成させるに至った。 In order to solve the above problems, the present inventors have made intensive studies. As a result, there is provided a polishing composition used for polishing an object to be polished including a silicon oxide film, the abrasive, a compound having a logarithmic value (LogP) of 1.0 or more of a distribution coefficient, It has been found that the above-mentioned problems can be solved by a polishing composition having a pH of less than 7, and the present invention has been completed.
本発明によれば、酸化ケイ素膜を含む研磨対象物の高い研磨速度を維持しつつ、酸化ケイ素膜を含む研磨対象物表面のスクラッチを十分に低減することができる研磨用組成物が提供される。 According to the present invention, there is provided a polishing composition that can sufficiently reduce scratches on the surface of a polishing target including a silicon oxide film while maintaining a high polishing rate of the polishing target including a silicon oxide film. .
本発明は、酸化ケイ素膜を含む研磨対象物を研磨するために用いられる研磨用組成物であって、砥粒と、分配係数の対数値（ＬｏｇＰ）が１．０以上である化合物と、分散媒と、を含有し、ｐＨが７未満である、研磨用組成物である。当該研磨用組成物によれば、酸化ケイ素膜を含む研磨対象物の高い研磨速度を維持しつつ、酸化ケイ素膜を含む研磨対象物表面のスクラッチを十分に低減することができる。 The present invention relates to a polishing composition used for polishing an object to be polished including a silicon oxide film, comprising an abrasive, a compound having a logarithmic value (LogP) of 1.0 or more of a distribution coefficient, and And a medium, and having a pH of less than 7. According to the polishing composition, scratches on the surface of the polishing target including the silicon oxide film can be sufficiently reduced while maintaining a high polishing rate of the polishing target including the silicon oxide film.
本発明の研磨用組成物により上記効果が得られる理由の詳細は不明であるが、下記のようなメカニズムが考えられる。ただし、下記メカニズムはあくまで推測であり、これによって本発明の範囲が限定されることはない。 The reason why the above-mentioned effects can be obtained by the polishing composition of the present invention is unknown, but the following mechanism is considered. However, the following mechanism is only speculation and does not limit the scope of the present invention.
特許文献１および２に記載の技術では、酸化ケイ素膜を含む研磨対象物表面のスクラッチを抑制することが十分ではなく、その原因について、本発明者らは鋭意検討を行った。その過程で、研磨パッドを用いて研磨対象物を研磨する際、研磨パッド屑が発生するが、研磨中のせん断応力により研磨パッド屑と砥粒とが凝集し、粗大粒子を作りやすくなり、この粗大粒子が原因となり、酸化ケイ素膜を含む研磨対象物表面のスクラッチが増加するのではないかと、本発明者らは考えた。 In the techniques described in Patent Literatures 1 and 2, it is not sufficient to suppress scratches on the surface of the object to be polished including the silicon oxide film, and the present inventors have conducted intensive studies on the cause. In the process, when polishing the object to be polished with the polishing pad, polishing pad debris is generated.However, the polishing stress is agglomerated with the polishing pad debris and the abrasive grains due to the shear stress during the polishing, which makes it easy to form coarse particles. The present inventors have thought that the scratches on the surface of the object to be polished including the silicon oxide film may increase due to the coarse particles.
このような課題に対し、本発明者らは、砥粒と、分配係数の対数値（ＬｏｇＰ、以下単に「ＬｏｇＰ」とも称する）が１．０以上である化合物と、分散媒と、を含有し、ｐＨが７未満である、研磨用組成物により上記課題が解決することを見出した。ＬｏｇＰが１．０以上である化合物は、一般に疎水部と親水部とを有しているが、研磨中に発生する研磨パッド屑の疎水性の表面に、疎水性相互作用で該化合物の疎水部が付着し、研磨パッド屑の表面は親水化される。表面が親水化された研磨パッド屑は、分散媒中（特に水中）で分散安定化し、砥粒との凝集が抑えられ、粗大粒子を形成しにくくなる。このようにして、研磨パッド屑と砥粒との粗大粒子の形成が抑制された本発明の研磨用組成物は、酸化ケイ素膜を含む研磨対象物の高い研磨速度を維持しつつ、酸化ケイ素膜を含む研磨対象物表面のスクラッチを十分に低減することができると考えられる。 In order to solve such a problem, the present inventors include an abrasive, a compound having a logarithmic value of a distribution coefficient (LogP, hereinafter simply referred to as “LogP”) of 1.0 or more, and a dispersion medium. It has been found that the above problem is solved by a polishing composition having a pH of less than 7. A compound having a LogP of 1.0 or more generally has a hydrophobic part and a hydrophilic part, but the hydrophobic part of the compound is formed on the hydrophobic surface of polishing pad debris generated during polishing by hydrophobic interaction. Adheres, and the surface of the polishing pad debris becomes hydrophilic. The polishing pad debris whose surface has been hydrophilized is dispersed and stabilized in a dispersion medium (particularly in water), aggregation with abrasive grains is suppressed, and it becomes difficult to form coarse particles. Thus, the polishing composition of the present invention in which the formation of coarse particles of polishing pad debris and abrasive grains is suppressed, while maintaining a high polishing rate of a polishing object including a silicon oxide film, a silicon oxide film It is considered that scratches on the surface of the object to be polished, including, can be sufficiently reduced.
以下、本発明の実施の形態を説明する。なお、本発明は、以下の実施の形態のみには限定されない。また、本明細書において、特記しない限り、操作および物性等の測定は室温（２０℃以上２５℃以下）／相対湿度４０％ＲＨ以上５０％ＲＨ以下の条件で行う。 Hereinafter, embodiments of the present invention will be described. Note that the present invention is not limited to only the following embodiments. In this specification, unless otherwise specified, the operation and measurement of physical properties are performed under the conditions of room temperature (20 ° C. or more and 25 ° C. or less) / relative humidity of 40% RH or more and 50% RH or less.
＜研磨対象物＞
［酸化ケイ素膜］
本発明に係る研磨対象物は、酸化ケイ素膜を有する。酸化ケイ素膜の例としては、たとえば、オルトケイ酸テトラエチルを前駆体として使用して生成されるＴＥＯＳ（Ｔｅｔｒａｅｔｈｙｌ Ｏｒｔｈｏｓｉｌｉｃａｔｅ）タイプ酸化ケイ素膜（以下、単に「ＴＥＯＳ」とも称する）、ＨＤＰ（Ｈｉｇｈ Ｄｅｎｓｉｔｙ Ｐｌａｓｍａ）膜、ＵＳＧ（Ｕｎｄｏｐｅｄ Ｓｉｌｉｃａｔｅ Ｇｌａｓｓ）膜、ＰＳＧ（Ｐｈｏｓｐｈｏｒｕｓ Ｓｉｌｉｃａｔｅ Ｇｌａｓｓ）膜、ＢＰＳＧ（Ｂｏｒｏｎ−Ｐｈｏｓｐｈｏ Ｓｉｌｉｃａｔｅ Ｇｌａｓｓ）膜、ＲＴＯ（Ｒａｐｉｄ Ｔｈｅｒｍａｌ Ｏｘｉｄａｔｉｏｎ）膜等が挙げられる。
<Object to be polished>
[Silicon oxide film]
The object to be polished according to the present invention has a silicon oxide film. Examples of the silicon oxide film include, for example, a tetraethyl orthosilicate (TEOS) type silicon oxide film (hereinafter, also simply referred to as “TEOS”) formed by using tetraethyl orthosilicate as a precursor, and an HDP (High Density Plasma) film. , USG (Undoped Silicate Glass) film, PSG (Phosphorus Silicate Glass) film, BPSG (Boron-Phospho Silicate Glass) film, RTO (Rapid Thermal Oxidation) film, and the like.
本発明に係る研磨対象物は、酸化ケイ素以外に、他の材料を含んでいてもよい。他の材料の例としては、窒化ケイ素、炭窒化ケイ素（ＳｉＣＮ）、多結晶シリコン（ポリシリコン）、非晶質シリコン（アモルファスシリコン）、金属、ＳｉＧｅ等が挙げられる。 The object to be polished according to the present invention may contain other materials in addition to silicon oxide. Examples of other materials include silicon nitride, silicon carbonitride (SiCN), polycrystalline silicon (polysilicon), amorphous silicon (amorphous silicon), metal, SiGe, and the like.
＜研磨用組成物＞
［砥粒］
本発明の研磨用組成物に使用される砥粒の種類としては、特に制限されず、たとえば、シリカ、アルミナ、ジルコニア、チタニア等の金属酸化物が挙げられる。該砥粒は、単独でもよいしまたは２種以上組み合わせても用いることができる。該砥粒は、それぞれ市販品を用いてもよいし合成品を用いてもよい。
<Polishing composition>
[Abrasive]
The type of abrasive used in the polishing composition of the present invention is not particularly limited, and examples thereof include metal oxides such as silica, alumina, zirconia, and titania. The abrasive grains may be used alone or in combination of two or more. Commercially available products or synthetic products may be used for the abrasive grains.
砥粒の種類としては、好ましくはシリカであり、より好ましくはコロイダルシリカである。コロイダルシリカの製造方法としては、ケイ酸ソーダ法、ゾルゲル法が挙げられ、いずれの製造方法で製造されたコロイダルシリカであっても、本発明の砥粒として好適に用いられる。しかしながら、金属不純物低減の観点から、ゾルゲル法により製造されたコロイダルシリカが好ましい。ゾルゲル法によって製造されたコロイダルシリカは、半導体中に拡散性のある金属不純物や塩化物イオン等の腐食性イオンの含有量が少ないため好ましい。ゾルゲル法によるコロイダルシリカの製造は、従来公知の手法を用いて行うことができ、具体的には、加水分解可能なケイ素化合物（たとえば、アルコキシシランまたはその誘導体）を原料とし、加水分解・縮合反応を行うことにより、コロイダルシリカを得ることができる。 The type of abrasive grains is preferably silica, and more preferably colloidal silica. Examples of the method for producing colloidal silica include a sodium silicate method and a sol-gel method. Colloidal silica produced by any of the production methods is suitably used as the abrasive grain of the present invention. However, colloidal silica produced by a sol-gel method is preferred from the viewpoint of reducing metal impurities. Colloidal silica produced by the sol-gel method is preferable because it has a low content of diffusible metal impurities and corrosive ions such as chloride ions in the semiconductor. The production of colloidal silica by the sol-gel method can be carried out using a conventionally known method. Specifically, a hydrolysis / condensation reaction is performed using a hydrolyzable silicon compound (for example, alkoxysilane or a derivative thereof) as a raw material. Is performed, colloidal silica can be obtained.
砥粒は、表面修飾していないシリカ（未変性シリカ）であってもよいが、カチオン性基を有するシリカ（カチオン変性シリカ）がさらに好ましく、カチオン性基を有するコロイダルシリカ（カチオン変性コロイダルシリカ）が特に好ましい。カチオン性基を有するシリカ（コロイダルシリカ）は、酸化ケイ素膜を含む研磨対象物の研磨速度をより向上させることができる。また、研磨パッド屑は一般に酸性条件下でゼータ電位がプラスであることから、ゼータ電位がプラスであるカチオン性基を有するシリカ（コロイダルシリカ）と研磨パッド屑との凝集はより抑制され、粗大粒子がより形成されにくくなり、研磨対象物表面のスクラッチをより低減することができる。 The abrasive may be silica having no surface modification (unmodified silica), but more preferably silica having a cationic group (cation modified silica), and more preferably colloidal silica having a cationic group (cation modified colloidal silica) Is particularly preferred. Silica having a cationic group (colloidal silica) can further improve the polishing rate of a polishing target including a silicon oxide film. In addition, since polishing pad debris generally has a positive zeta potential under acidic conditions, aggregation between silica (colloidal silica) having a cationic group having a positive zeta potential and polishing pad debris is further suppressed, and coarse particles are removed. Are less likely to be formed, and scratches on the surface of the object to be polished can be further reduced.
カチオン性基を有するコロイダルシリカ（カチオン変性コロイダルシリカ）としては、アミノ基が表面に固定化されたコロイダルシリカが好ましく挙げられる。このようなカチオン性基を有するコロイダルシリカの製造方法としては、特開２００５−１６２５３３号公報に記載されているような、アミノエチルトリメトキシシラン、アミノプロピルトリメトキシシラン、アミノエチルトリエトキシシラン、アミノプロピルトリエトキシシラン、アミノプロピルジメチルエトキシシラン、アミノプロピルメチルジエトキシシラン、アミノブチルトリエトキシシラン等のアミノ基を有するシランカップリング剤を砥粒の表面に固定化する方法が挙げられる。これにより、アミノ基が表面に固定化されたコロイダルシリカを得ることができる。 As the colloidal silica having a cationic group (cation-modified colloidal silica), a colloidal silica having an amino group immobilized on the surface is preferably exemplified. Examples of a method for producing colloidal silica having such a cationic group include aminoethyltrimethoxysilane, aminopropyltrimethoxysilane, aminoethyltriethoxysilane, and aminoethyltrimethoxysilane as described in JP-A-2005-162533. A method of immobilizing a silane coupling agent having an amino group, such as propyltriethoxysilane, aminopropyldimethylethoxysilane, aminopropylmethyldiethoxysilane, and aminobutyltriethoxysilane, on the surface of the abrasive grains is exemplified. Thus, colloidal silica having amino groups immobilized on the surface can be obtained.
砥粒の形状は、特に制限されず、球形状であってもよいし、非球形状であってもよい。非球形状の具体例としては、三角柱や四角柱などの多角柱状、円柱状、円柱の中央部が端部よりも膨らんだ俵状、円盤の中央部が貫通しているドーナツ状、板状、中央部にくびれを有するいわゆる繭型形状、複数の粒子が一体化しているいわゆる会合型球形状、表面に複数の突起を有するいわゆる金平糖形状、ラグビーボール形状等、種々の形状が挙げられ、特に制限されない。 The shape of the abrasive grains is not particularly limited, and may be spherical or non-spherical. Specific examples of the non-spherical shape include polygonal prisms such as triangular prisms and quadrangular prisms, cylindrical shapes, bale shapes in which the central portion of the cylinder bulges from the ends, donut shapes in which the central portion of the disk penetrates, plate shapes, Various shapes such as a so-called cocoon shape having a constriction in the center, a so-called associative sphere shape in which a plurality of particles are integrated, a so-called confetti shape having a plurality of protrusions on the surface, and a rugby ball shape, are particularly limited. Not done.
砥粒の大きさは特に制限されないが、砥粒の平均一次粒子径の下限は、５ｎｍ以上であることが好ましく、７ｎｍ以上であることがより好ましく、１０ｎｍ以上であることがさらに好ましい。また、本発明の研磨用組成物中、砥粒の平均一次粒子径の上限は、１２０ｎｍ以下が好ましく、８０ｎｍ以下がより好ましく、５０ｎｍ以下がさらに好ましい。このような範囲であれば、研磨用組成物を用いて研磨した後の研磨対象物の表面にスクラッチなどのディフェクトを抑えることができる。すなわち、砥粒の平均一次粒子径は、５ｎｍ以上１２０ｎｍ以下であることが好ましく、７ｎｍ以上８０ｎｍ以下であることがより好ましく、１０ｎｍ以上５０ｎｍ以下であることがさらに好ましい。なお、砥粒の平均一次粒子径は、たとえば、ＢＥＴ法で測定される砥粒の比表面積に基づいて算出される。 The size of the abrasive grains is not particularly limited, but the lower limit of the average primary particle diameter of the abrasive grains is preferably 5 nm or more, more preferably 7 nm or more, and even more preferably 10 nm or more. In the polishing composition of the present invention, the upper limit of the average primary particle diameter of the abrasive grains is preferably 120 nm or less, more preferably 80 nm or less, and further preferably 50 nm or less. Within such a range, defects such as scratches on the surface of the object to be polished after polishing with the polishing composition can be suppressed. That is, the average primary particle diameter of the abrasive grains is preferably from 5 nm to 120 nm, more preferably from 7 nm to 80 nm, even more preferably from 10 nm to 50 nm. The average primary particle diameter of the abrasive grains is calculated based on, for example, the specific surface area of the abrasive grains measured by the BET method.
本発明の研磨用組成物中、砥粒の平均二次粒子径の下限は、１０ｎｍ以上であることが好ましく、２０ｎｍ以上であることがより好ましく、３０ｎｍ以上であることがさらに好ましい。また、本発明の研磨用組成物中、砥粒の平均二次粒子径の上限は、２５０ｎｍ以下が好ましく、２００ｎｍ以下がより好ましく、１５０ｎｍ以下がさらに好ましい。このような範囲であれば、研磨用組成物を用いて研磨した後の研磨対象物の表面にスクラッチなどのディフェクトを抑えることができる。すなわち、砥粒の平均二次粒子径は、１０ｎｍ以上２５０ｎｍ以下であることが好ましく、２０ｎｍ以上２００ｎｍ以下であることがより好ましく、３０ｎｍ以上１５０ｎｍ以下であることがさらに好ましい。なお、砥粒の平均二次粒子径は、たとえば、レーザー回折散乱法に代表される動的光散乱法により測定することができる。 In the polishing composition of the present invention, the lower limit of the average secondary particle diameter of the abrasive grains is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more. In the polishing composition of the present invention, the upper limit of the average secondary particle diameter of the abrasive grains is preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. Within such a range, defects such as scratches on the surface of the object to be polished after polishing with the polishing composition can be suppressed. That is, the average secondary particle diameter of the abrasive grains is preferably 10 nm or more and 250 nm or less, more preferably 20 nm or more and 200 nm or less, and even more preferably 30 nm or more and 150 nm or less. The average secondary particle diameter of the abrasive grains can be measured, for example, by a dynamic light scattering method represented by a laser diffraction scattering method.
砥粒の平均会合度は、５．０以下であることが好ましく、３．０以下であることがより好ましく、２．５以下であることがさらに好ましい。砥粒の平均会合度が小さくなるにつれて、研磨対象物表面の欠陥発生をより低減することができる。また、砥粒の平均会合度は、１．０以上であることが好ましく、１．２以上であることがより好ましい。砥粒の平均会合度が大きくなるにつれて、研磨用組成物による研磨速度が向上する利点がある。なお、砥粒の平均会合度は、砥粒の平均二次粒子径の値を平均一次粒子径の値で除することにより得られる。 The average degree of association of the abrasive grains is preferably 5.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. As the average degree of association of the abrasive grains decreases, the occurrence of defects on the surface of the object to be polished can be further reduced. The average degree of association of the abrasive grains is preferably 1.0 or more, and more preferably 1.2 or more. As the average degree of association of the abrasive grains increases, there is an advantage that the polishing rate by the polishing composition is improved. The average degree of association of the abrasive grains is obtained by dividing the value of the average secondary particle diameter of the abrasive grains by the value of the average primary particle diameter.
砥粒のアスペクト比の上限は、特に制限されないが、２．０未満であることが好ましく、１．８以下であることがより好ましく、１．５以下であることがさらに好ましい。このような範囲であれば、研磨対象物表面の欠陥をより低減することができる。なお、アスペクト比は、走査型電子顕微鏡により砥粒粒子の画像に外接する最小の長方形をとり、その長方形の長辺の長さを同じ長方形の短辺の長さで除することにより得られる値の平均であり、一般的な画像解析ソフトウエアを用いて求めることができる。砥粒のアスペクト比の下限は、特に制限されないが、１．０以上であることが好ましい。 The upper limit of the aspect ratio of the abrasive grains is not particularly limited, but is preferably less than 2.0, more preferably 1.8 or less, and even more preferably 1.5 or less. Within such a range, defects on the surface of the object to be polished can be further reduced. The aspect ratio is a value obtained by taking the smallest rectangle circumscribing the image of the abrasive grains using a scanning electron microscope and dividing the length of the long side of the rectangle by the length of the short side of the same rectangle. And can be determined using general image analysis software. The lower limit of the aspect ratio of the abrasive grains is not particularly limited, but is preferably 1.0 or more.
砥粒のレーザー回折散乱法により求められる粒度分布において、微粒子側から積算粒子重量が全粒子重量の９０％に達するときの粒子の直径（Ｄ９０）と全粒子の全粒子重量の１０％に達するときの粒子の直径（Ｄ１０）との比であるＤ９０／Ｄ１０の下限は、特に制限されないが、１．１以上であることが好ましく、１．２以上であることがより好ましく、１．３以上であることがさらに好ましい。また、研磨用組成物中の砥粒における、レーザー回折散乱法により求められる粒度分布において、微粒子側から積算粒子重量が全粒子重量の９０％に達するときの粒子の直径（Ｄ９０）と全粒子の全粒子重量の１０％に達するときの粒子の直径（Ｄ１０）との比Ｄ９０／Ｄ１０の上限は特に制限されないが、２．０４以下であることが好ましい。このような範囲であれば、研磨対象物表面の欠陥をより低減することができる。 In the particle size distribution obtained by the laser diffraction scattering method of abrasive grains, when the cumulative particle weight from the fine particle side reaches 90% of the total particle weight (D90) and when the particle weight reaches 10% of the total particle weight of all the particles The lower limit of D90 / D10, which is the ratio to the diameter (D10) of the particles, is not particularly limited, but is preferably 1.1 or more, more preferably 1.2 or more, and 1.3 or more. It is more preferred that there be. In the particle size distribution obtained by the laser diffraction scattering method in the abrasive grains in the polishing composition, the diameter (D90) of the particles when the integrated particle weight reaches 90% of the total particle weight from the fine particle side and the total particle weight The upper limit of the ratio D90 / D10 to the diameter (D10) of the particles when reaching 10% of the total particle weight is not particularly limited, but is preferably 2.04 or less. Within such a range, defects on the surface of the object to be polished can be further reduced.
砥粒の大きさ（平均一次粒子径、平均二次粒子径、アスペクト比、Ｄ９０／Ｄ１０等）は、砥粒の製造方法の選択等により適切に制御することができる。 The size of the abrasive grains (average primary particle diameter, average secondary particle diameter, aspect ratio, D90 / D10, etc.) can be appropriately controlled by selecting a method for producing the abrasive grains.
本発明の研磨用組成物中の砥粒の含有量（濃度）の下限は、０．０１質量％以上であることが好ましく、０．０５質量％以上であることがより好ましく、０．１質量％以上であることがさらに好ましい。また、本発明の研磨用組成物中、砥粒の含有量の上限は、２０質量％以下であることが好ましく、１０質量％以下であることがより好ましく、５質量％以下であることがさらに好ましく、３質量％以下であることがよりさらに好ましい。上限がこのようであると、研磨用組成物を用いて研磨した後の研磨対象物の表面に表面欠陥が生じるのをより抑えることができる。なお、研磨用組成物が２種以上の砥粒を含む場合には、砥粒の含有量はこれらの合計量を意図する。 The lower limit of the content (concentration) of the abrasive grains in the polishing composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass. % Is more preferable. In the polishing composition of the present invention, the upper limit of the content of the abrasive grains is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. It is more preferably at most 3% by mass. With such an upper limit, the occurrence of surface defects on the surface of the object to be polished after polishing with the polishing composition can be further suppressed. When the polishing composition contains two or more types of abrasive grains, the content of the abrasive grains intends the total amount of these.
［分配係数の対数値（ＬｏｇＰ）が１．０以上である化合物（スクラッチ低減剤）］
本発明の研磨用組成物は、分配係数の対数値（ＬｏｇＰ、以下単に「ＬｏｇＰ」とも称する）が１．０以上である化合物（以下、「スクラッチ低減剤」とも称する）を含む。スクラッチ低減剤は、研磨中に発生する疎水性の研磨パッド屑の表面に付着し、研磨パッド屑の表面を親水化する。これにより、研磨パッド屑と砥粒との粗大粒子の形成が抑制され、酸化ケイ素膜を含む研磨対象物の高い研磨速度を維持しつつ、酸化ケイ素膜を含む研磨対象物表面のスクラッチを十分に低減することができる。
[Compound having logarithmic value (LogP) of distribution coefficient of 1.0 or more (scratch reducing agent)]
The polishing composition of the present invention contains a compound having a logarithmic value of distribution coefficient (LogP, hereinafter simply referred to as “LogP”) of 1.0 or more (hereinafter, also referred to as “scratch reducing agent”). The scratch reducing agent adheres to the surface of the hydrophobic polishing pad debris generated during polishing, and makes the surface of the polishing pad debris hydrophilic. Thereby, the formation of coarse particles of polishing pad debris and abrasive grains is suppressed, and while maintaining the high polishing rate of the polishing target including the silicon oxide film, the scratch on the polishing target surface including the silicon oxide film can be sufficiently scratched. Can be reduced.
ここで「ＬｏｇＰ」とは、水と１−オクタノールとに対する有機化合物の親和性を示す値である。１−オクタノール／水の分配係数Ｐは、１−オクタノールと水との二液相の溶媒に微量の化合物が溶質として溶け込んだときの分配平衡で、それぞれの溶媒中における化合物の平衡濃度の比であり、底１０に対するそれらの対数ＬｏｇＰで示す。すなわち、「ＬｏｇＰ」とは、１−オクタノール／水の分配係数Ｐの対数値であり、分子の親疎水性を表すパラメータとして知られている。 Here, “LogP” is a value indicating the affinity of an organic compound for water and 1-octanol. The partition coefficient P of 1-octanol / water is a partition equilibrium when a trace amount of a compound is dissolved as a solute in a solvent in a two liquid phase of 1-octanol and water, and is a ratio of the equilibrium concentration of the compound in each solvent. And their logarithm LogP relative to the base 10. That is, “LogP” is a logarithmic value of the partition coefficient P of 1-octanol / water, and is known as a parameter indicating the hydrophilic / hydrophobic property of the molecule.
なお、本明細書において、分配係数の対数値（ＬｏｇＰ）は、ＡＣＤ／ＰｈｙＣｈｅｍ Ｓｕｉｔｅ（ＡＣＤ／Ｌａｂｓ）を用いて化学物質の構造から算出している。 In this specification, the logarithmic value (LogP) of the distribution coefficient is calculated from the structure of a chemical substance using ACD / PhyChem Suite (ACD / Labs).
本発明で用いられるスクラッチ低減剤のＬｏｇＰは、１．０以上である。ＬｏｇＰが１．０未満の場合、疎水性相互作用による研磨パッド屑への吸着が起こり難く、粗大粒子の形成を抑制できない。 LogP of the scratch reducing agent used in the present invention is 1.0 or more. When LogP is less than 1.0, adsorption to polishing pad debris due to hydrophobic interaction hardly occurs, and formation of coarse particles cannot be suppressed.
ＬｏｇＰが１．０以上であるスクラッチ低減剤の具体的な例を以下に挙げる。なお、化合物名の後ろに示すカッコ内の数値は、ＬｏｇＰの値である。 Specific examples of the scratch reducing agent having a LogP of 1.0 or more are described below. The numerical value in parentheses after the compound name is the value of LogP.
イソ酪酸（１．０）、２−アミノフェノール（１．０）、ジプロピレングリコールジメチルエーテル（１．０２）、２，５−ジヒドロキシテレフタル酸（１．１）、２−フェノキシエタノール（１．１）、ジプロピレングリコールモノブチルエーテル（１．１３）、３，５−ジメチルチアゾール（１．１８）、２−ペンタノール（１．１９）、プロピレングリコールモノブチルエーテル（１．１９）、ジエチレングリコールモノブチルエーテル（１．１９）、ベンゾトリアゾール（１．２２）、２−ペンチルグリセリルエーテル（１．２５）、Ｎ−４−ヒドロキシフェニルグリシン（１．３）、１，２−オクタンジオール（１．３）、イソ吉草酸（１．３）、ソルビタンモノカプリレート（１．３３）、トリプロピレングリコールモノブチルエーテル（１．３４）、没食子酸エチル（１．４）、１−ペンタノール（１．４）、トリプロピレングリコールジメチルエーテル（１．４６）、２−ヒドロキシエチルサリチレート（１．５）、４−ヒドロキシベンゼンスルホン酸（１．５）、トランスフェルラ酸（１．５）、２，４−ジヒドロキシ安息香酸（１．５）、１，２−ヘプタンジオール（１．５）、１−フェノキシ−２−プロパノール（１．５２）、１，２−オクタンジオール（１．５４）、エチレングリコールモノ−ｎ−ヘキシルエーテル（１．５７）、ｐ−クマル酸（１．６）、３−ヒドロキシ安息香酸（１．６）、２，５−ジヒドロキシ安息香酸（１．６）、２，６−ジヒドロキシ安息香酸（１．６）、エチレングリコールモノへキシルエーテル（１．７）、ジエチレングリコールモノヘキシルエーテル（１．７）、プロピレングリコールジプロピオネート（１．７６）、エチレングリコールモノブチルエーテルアセテート（１．７９）、ジエチレングリコールジ−ｎ−ブチルエーテル（１．９２）、２−エチルヘキシルグリセリルエーテル（２．０）、アジピン酸ジイソプロピル（２．０４）、１−オクチルグリセリルエーテル（２．１）、サリチル酸（２．１）、３−クロロ−４−ヒドロキシ安息香酸（２．１）、２，４−ジメチルチアゾール（２．１５）、５−クロロサリチル酸（２．３）、エチレングリコールモノ（２−エチルヘキシル）エーテル（２．４６）、１−フェニル−５−メルカプトテトラゾール（２．５６）、３，５−ジクロロ−４−ヒドロキシ安息香酸（２．８）、ジメチルラウリルアミンオキシド（３．０９）、ショ糖ラウリン酸エステル（３．１８）、１，３−ジフェニルグアニジン（３．３４）、ソルビタンモノラウレート（３．３７）、ミリスチン酸イソプロピル（４．４２）、テトラデカナール（４．６７）、ラウリン酸ナトリウム（４．７７）、ミリスチン酸（４．９４）、ショ糖パルミチン酸エステル（５．２２）、サリチル酸オクチル（５．４）、プロピレングリコールジカプリラート（５．４７）、１−メチルウンデカン（５．５１）、ショ糖オレイン酸エステル（５．８５）、リシノール酸（５．９）、ステアリン酸（６．６１）、オレイン酸ジエタノールアミド（６．６８）、２−ヘキシル−１−デカノール（６．８）、オレイン酸（７．０）、トリエチルヘキサノイン（７．０５）、オレイン酸ナトリウム（７．４２）、フィトール（８．０）、パルミチン酸イソオクチル（８．８６）、トリ（カプリル酸／カプリン酸）グリセリド（９．２５）、酢酸トコフェロール（１０．６１）。 Isobutyric acid (1.0), 2-aminophenol (1.0), dipropylene glycol dimethyl ether (1.02), 2,5-dihydroxyterephthalic acid (1.1), 2-phenoxyethanol (1.1), Dipropylene glycol monobutyl ether (1.13), 3,5-dimethylthiazole (1.18), 2-pentanol (1.19), propylene glycol monobutyl ether (1.19), diethylene glycol monobutyl ether (1.19) ), Benzotriazole (1.22), 2-pentylglyceryl ether (1.25), N-4-hydroxyphenylglycine (1.3), 1,2-octanediol (1.3), isovaleric acid ( 1.3), sorbitan monocaprylate (1.33), tripropylene glycol monobutyl -(1.34), ethyl gallate (1.4), 1-pentanol (1.4), tripropylene glycol dimethyl ether (1.46), 2-hydroxyethyl salicylate (1.5), 4 -Hydroxybenzenesulfonic acid (1.5), transferuric acid (1.5), 2,4-dihydroxybenzoic acid (1.5), 1,2-heptanediol (1.5), 1-phenoxy-2 -Propanol (1.52), 1,2-octanediol (1.54), ethylene glycol mono-n-hexyl ether (1.57), p-coumaric acid (1.6), 3-hydroxybenzoic acid ( 1.6), 2,5-dihydroxybenzoic acid (1.6), 2,6-dihydroxybenzoic acid (1.6), ethylene glycol monohexyl ether (1.7), diethylene glycol Chole monohexyl ether (1.7), propylene glycol dipropionate (1.76), ethylene glycol monobutyl ether acetate (1.79), diethylene glycol di-n-butyl ether (1.92), 2-ethylhexyl glyceryl ether ( 2.0), diisopropyl adipate (2.04), 1-octylglyceryl ether (2.1), salicylic acid (2.1), 3-chloro-4-hydroxybenzoic acid (2.1), 2,4 -Dimethylthiazole (2.15), 5-chlorosalicylic acid (2.3), ethylene glycol mono (2-ethylhexyl) ether (2.46), 1-phenyl-5-mercaptotetrazole (2.56), 3, 5-dichloro-4-hydroxybenzoic acid (2.8), dimethyllaurylamine Oxide (3.09), sucrose laurate (3.18), 1,3-diphenylguanidine (3.34), sorbitan monolaurate (3.37), isopropyl myristate (4.42), tetra Decanal (4.67), sodium laurate (4.77), myristic acid (4.94), sucrose palmitate (5.22), octyl salicylate (5.4), propylene glycol dicaprylate ( 5.47), 1-methylundecane (5.51), sucrose oleate (5.85), ricinoleic acid (5.9), stearic acid (6.61), oleic acid diethanolamide (6.68) ), 2-hexyl-1-decanol (6.8), oleic acid (7.0), triethylhexanoin (7.05), sodium oleate (7.42), phytol (8.0), isooctyl palmitate (8.86), tri (caprylic acid / capric acid) glyceride (9.25), tocopherol acetate (10.61).
該スクラッチ低減剤は、単独でもまたは２種以上混合しても用いることができる。また、該スクラッチ低減剤は、合成品を用いてもよいし市販品を用いてもよい。 The scratch reducing agent can be used alone or in combination of two or more. Further, as the scratch reducing agent, a synthetic product or a commercially available product may be used.
スクラッチ低減剤のＬｏｇＰの下限は、スクラッチをより少なくするという観点から、１．１以上であることが好ましく、１．２以上であることがより好ましく、１．３以上であることがさらに好ましく、１．３超であることが特に好ましい。また、スクラッチ低減剤のＬｏｇＰの上限は、特に制限されないが、研磨パッド屑の分散安定性をさらに高めるという観点から、７．０以下であることが好ましく、５．０以下であることがより好ましく、４．０以下であることがさらに好ましい。 The lower limit of LogP of the scratch reducing agent is preferably 1.1 or more, more preferably 1.2 or more, still more preferably 1.3 or more, from the viewpoint of reducing scratches. It is particularly preferred that it is more than 1.3. Although the upper limit of LogP of the scratch reducing agent is not particularly limited, it is preferably 7.0 or less, more preferably 5.0 or less, from the viewpoint of further increasing the dispersion stability of the polishing pad debris. , More preferably 4.0 or less.
また、当該スクラッチ低減剤は、界面活性剤であることが好ましい。スクラッチ低減剤が界面活性剤であれば、界面活性効果が得られるという利点を有する。かような界面活性剤であるスクラッチ低減剤の例としては、たとえば、ソルビタンモノカプリレート（１．３３）、ジメチルラウリルアミンオキシド（３．０９）、ショ糖ラウリン酸エステル（３．１８）、ソルビタンモノラウレート（３．３７）、ラウリン酸ナトリウム（４．７７）、ショ糖パルミチン酸エステル（５．２２）、ショ糖オレイン酸エステル（５．８５）、オレイン酸ジエタノールアミド（６．６８）、オレイン酸ナトリウム（７．４２）、パルミチン酸イソオクチル（８．８６）等が挙げられる。 Further, the scratch reducing agent is preferably a surfactant. If the scratch reducing agent is a surfactant, there is an advantage that a surfactant effect can be obtained. Examples of such a surfactant as a scratch reducing agent include, for example, sorbitan monocaprylate (1.33), dimethyllaurylamine oxide (3.09), sucrose laurate (3.18), sorbitan Monolaurate (3.37), sodium laurate (4.77), sucrose palmitate (5.22), sucrose oleate (5.85), diethanolamide oleate (6.68), And sodium oleate (7.42), isooctyl palmitate (8.86) and the like.
さらに、当該スクラッチ低減剤は、硫黄原子を有しないことが好ましい。硫黄原子を有するスクラッチ低減剤は、疎水性が高く、水への分散安定性が低下してしまう。また、ｐＨ７未満の条件では、研磨パッド屑は正に帯電しており、硫黄原子を有するスクラッチ低減剤の親水部（主として硫黄原子を有するオキソ酸部分）は、負に帯電する。そのため、スクラッチ低減剤の疎水部ではなく、スクラッチ低減剤の硫黄原子を有する親水部（主として硫黄原子を有するオキソ酸部分）が静電的に研磨パッド屑に吸着してしまい、研磨パッド屑の親水化効果を低減させる。一方、水酸基やカルボン酸基のような官能基を有し、硫黄原子を有しないスクラッチ低減剤は、水への分散安定性が高いことに加え、硫黄原子を有しないスクラッチ低減剤の親水部（水酸基やカルボン酸基）は、硫黄原子を有する親水部（オキソ酸部分）と比較して電離度が低い。よって、硫黄原子を有しないスクラッチ低減剤の親水部の帯電は、硫黄原子を有する親水部（オキソ酸部分）の帯電と比べて小さくなる。そのため硫黄原子を有しないスクラッチ低減剤の親水部が研磨パッド屑表面に静電的に吸着する度合は、硫黄原子を有する親水部と比べ低くなり、研磨パッド屑との疎水性相互作用による吸着度合が高くなる。よって、硫黄原子を有しないスクラッチ低減剤は、研磨パッド屑の親水化効果をより高めることができ、本発明の効果がより向上する。同様の観点から、スクラッチ低減剤は、硫黄原子と窒素原子との両方を有しないことがより好ましい。 Further, it is preferable that the scratch reducing agent does not have a sulfur atom. A scratch reducing agent having a sulfur atom has high hydrophobicity, and the dispersion stability in water is reduced. Further, under the condition of less than pH 7, the polishing pad debris is positively charged, and the hydrophilic portion (mainly the oxo acid portion having a sulfur atom) of the scratch reducing agent having a sulfur atom is negatively charged. Therefore, not the hydrophobic part of the scratch reducing agent but the hydrophilic part having a sulfur atom (mainly the oxo acid part having a sulfur atom) of the scratch reducing agent is electrostatically adsorbed to the polishing pad debris, and the hydrophilicity of the polishing pad debris is increased. Reduction effect. On the other hand, a scratch reducing agent having a functional group such as a hydroxyl group or a carboxylic acid group and having no sulfur atom has a high dispersion stability in water and, in addition to the hydrophilic portion of the scratch reducing agent having no sulfur atom ( A hydroxyl group or a carboxylic acid group has a lower ionization degree than a hydrophilic portion having a sulfur atom (oxo acid portion). Therefore, the charge of the hydrophilic portion of the scratch reducing agent having no sulfur atom is smaller than the charge of the hydrophilic portion having a sulfur atom (oxo acid portion). Therefore, the degree to which the hydrophilic part of the scratch reducing agent having no sulfur atom is electrostatically adsorbed to the polishing pad debris surface is lower than that of the hydrophilic part having the sulfur atom, and the degree of adsorption by the hydrophobic interaction with the polishing pad debris is reduced. Will be higher. Therefore, the scratch reducing agent having no sulfur atom can further enhance the effect of hydrophilizing the polishing pad debris, and the effect of the present invention is further improved. From the same viewpoint, it is more preferable that the scratch reducing agent does not have both a sulfur atom and a nitrogen atom.
スクラッチ低減剤の含有量（濃度）は特に制限されないが、研磨用組成物の総質量に対して、１質量ｐｐｍ以上であることが好ましく、１０質量ｐｐｍ以上であることがより好ましく、３０質量ｐｐｍ以上であることがさらに好ましい。また、スクラッチ低減剤の含有量（濃度）の上限は、研磨用組成物の総質量に対して、１００００質量ｐｐｍ以下であることが好ましく、５０００質量ｐｐｍ以下であることがより好ましく、３０００質量ｐｐｍ以下であることがさらに好ましい。すなわち、スクラッチ低減剤の含有量（濃度）は、研磨用組成物の総質量に対して、好ましくは１質量ｐｐｍ以上１００００質量ｐｐｍ以下、より好ましくは１０質量ｐｐｍ以上５０００質量ｐｐｍ以下、さらに好ましくは３０質量ｐｐｍ以上３０００質量ｐｐｍ以下である。このような範囲であれば、高い研磨速度を維持しつつスクラッチを低減するという本発明の効果が効率よく得られる。なお、研磨用組成物が２種以上のスクラッチ低減剤を含む場合には、スクラッチ低減剤の含有量はこれらの合計量を意図する。 Although the content (concentration) of the scratch reducing agent is not particularly limited, it is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, and more preferably 30 mass ppm, based on the total mass of the polishing composition. More preferably, it is the above. Further, the upper limit of the content (concentration) of the scratch reducing agent is preferably 10,000 mass ppm or less, more preferably 5000 mass ppm or less, and more preferably 3000 mass ppm with respect to the total mass of the polishing composition. It is more preferred that: That is, the content (concentration) of the scratch reducing agent is preferably 1 mass ppm or more and 10,000 mass ppm or less, more preferably 10 mass ppm or more and 5000 mass ppm or less, and still more preferably the total mass of the polishing composition. 30 mass ppm or more and 3000 mass ppm or less. Within such a range, the effect of the present invention of reducing scratches while maintaining a high polishing rate can be obtained efficiently. When the polishing composition contains two or more types of scratch reducing agents, the content of the scratch reducing agent intends the total amount of these.
［分散媒］
本発明の研磨用組成物は、研磨用組成物を構成する各成分の分散のために分散媒が用いられる。分散媒としては、有機溶媒、水が挙げられるが、その中でも水を含むことが好ましい。
[Dispersion medium]
In the polishing composition of the present invention, a dispersion medium is used for dispersing each component constituting the polishing composition. Examples of the dispersion medium include an organic solvent and water, and among them, water is preferable.
研磨対象物の汚染や他の成分の作用を阻害することを抑制するという観点から、分散媒としては不純物をできる限り含有しない水が好ましい。このような水としては、たとえば、遷移金属イオンの合計含有量が１００ｐｐｂ以下である水が好ましい。ここで、水の純度は、たとえば、イオン交換樹脂を用いる不純物イオンの除去、フィルタによる異物の除去、蒸留等の操作によって高めることができる。具体的には、水としては、たとえば、脱イオン水（イオン交換水）、純水、超純水、蒸留水などを用いることが好ましい。通常は、研磨用組成物に含まれる分散媒の９０体積％以上が水であることが好ましく、９５体積％以上が水であることがより好ましく、９９体積％以上が水であることがさらに好ましく、１００体積％が水であることが特に好ましい。 From the viewpoint of suppressing the contamination of the object to be polished and inhibiting the action of other components, water that does not contain impurities as much as possible is preferable as the dispersion medium. As such water, for example, water having a total content of transition metal ions of 100 ppb or less is preferable. Here, the purity of water can be increased by operations such as removal of impurity ions using an ion exchange resin, removal of foreign matter by a filter, and distillation. Specifically, as the water, for example, it is preferable to use deionized water (ion-exchanged water), pure water, ultrapure water, distilled water, or the like. Usually, 90% by volume or more of the dispersion medium contained in the polishing composition is preferably water, more preferably 95% by volume or more is water, and even more preferably 99% by volume or more is water. It is particularly preferred that 100% by volume is water.
［研磨用組成物のｐＨ］
本発明の研磨用組成物のｐＨは、７未満である。ｐＨが７以上であると、酸化ケイ素膜を含む研磨対象物表面のスクラッチ低減の効果が得られない。また、酸化ケイ素膜を含む研磨対象物の研磨レートも低下する。該ｐＨは、６．５以下、６以下、５．５以下、５．０以下、５．０未満、４．０以下、３．５以下であってもよい。また、該ｐＨの下限は、１以上、１．５以上、２以上、２．５以上、３以上、３．５以上であってもよい。
[PH of polishing composition]
The polishing composition of the present invention has a pH of less than 7. When the pH is 7 or more, the effect of reducing scratches on the surface of the polishing target including the silicon oxide film cannot be obtained. Further, the polishing rate of the object to be polished including the silicon oxide film also decreases. The pH may be 6.5 or less, 6 or less, 5.5 or less, 5.0 or less, less than 5.0, 4.0 or less, 3.5 or less. The lower limit of the pH may be 1 or more, 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more.
なお、砥粒として、表面修飾していないシリカ（未変性シリカ）を用いる場合、研磨用組成物のｐＨは、１．５以上３．５以下が好ましい。また、砥粒として、カチオン変性シリカを用いる場合、研磨用組成物のｐＨは、３．５以上５．５以下が好ましい。 In addition, when using silica without surface modification (unmodified silica) as the abrasive, the pH of the polishing composition is preferably 1.5 or more and 3.5 or less. When cation-modified silica is used as the abrasive, the pH of the polishing composition is preferably 3.5 or more and 5.5 or less.
なお、研磨用組成物のｐＨは、実施例に記載の方法により測定することができる。 The pH of the polishing composition can be measured by the method described in Examples.
（ｐＨ調整剤、ｐＨ緩衝剤）
本発明に係る研磨用組成物は、ｐＨを上記範囲内に調整する目的で、ｐＨ調整剤をさらに含んでいてもよい。
(PH adjuster, pH buffer)
The polishing composition according to the present invention may further contain a pH adjuster for the purpose of adjusting the pH within the above range.
ｐＨ調整剤としては、公知の酸、塩基、またはこれらの塩を使用することができる。ｐＨ調整剤として使用できる酸の具体例としては、たとえば、塩酸、硫酸、硝酸、フッ酸、ホウ酸、炭酸、次亜リン酸、亜リン酸、およびリン酸等の無機酸や、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、グリコール酸、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、乳酸、ジグリコール酸、２−フランカルボン酸、２，５−フランジカルボン酸、３−フランカルボン酸、２−テトラヒドロフランカルボン酸、メトキシ酢酸、メトキシフェニル酢酸、フェノキシ酢酸、およびエチドロン酸（１−ヒドロキシエタン−１，１−ジホスホン酸、ＨＥＤＰ）等の有機酸が挙げられる。 Known acids, bases, or salts thereof can be used as the pH adjuster. Specific examples of acids that can be used as a pH adjuster include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid, formic acid, and 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, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid Acid, lactic acid, diglycolic acid, 2-furancarboxylic acid, 2,5-furandicarboxylic acid, 3-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, methoxyacetic acid, methoxy Phenylacetic acid, phenoxyacetic acid, and etidronate (1-hydroxyethane-1,1-diphosphonic acid, HEDP) and organic acids such as.
ｐＨ調整剤として使用できる塩基としては、エタノールアミン、２−アミノ−２−エチル−１，３−プロパンジオール等の脂肪族アミン、芳香族アミン等のアミン、水酸化第四アンモニウムなどの有機塩基、水酸化カリウム等のアルカリ金属の水酸化物、アルカリ土類金属の水酸化物、水酸化テトラメチルアンモニウム、アンモニア等が挙げられる。 Examples of the base that can be used as a pH adjuster include aliphatic amines such as ethanolamine, 2-amino-2-ethyl-1,3-propanediol, amines such as aromatic amines, and organic bases such as quaternary ammonium hydroxide. Examples include alkali metal hydroxides such as potassium hydroxide, alkaline earth metal hydroxides, tetramethylammonium hydroxide, and ammonia.
上記ｐＨ調整剤は、単独でもまたは２種以上混合しても用いることができる。 The pH adjusters can be used alone or in combination of two or more.
また、上記の酸と組み合わせて、上記酸のアンモニウム塩や、ナトリウム塩、カリウム塩等のアルカリ金属塩をｐＨ緩衝剤として用いてもよい。 Further, in combination with the above acid, an alkali metal salt such as an ammonium salt, a sodium salt, or a potassium salt of the above acid may be used as a pH buffer.
ｐＨ調整剤およびｐＨ緩衝剤の添加量は、特に制限されず、研磨用組成物のｐＨが所望の範囲内となるよう適宜調整すればよい。 The amounts of the pH adjuster and the pH buffer added are not particularly limited, and may be appropriately adjusted so that the pH of the polishing composition falls within a desired range.
［その他の添加剤］
本発明の研磨用組成物は、本発明の効果を損なわない範囲において、キレート剤、増粘剤、酸化剤、分散剤、表面保護剤、濡れ剤、ＬｏｇＰが１．０未満である界面活性剤、防錆剤、防腐剤、防カビ剤等の公知の添加剤をさらに含有してもよい。上記添加剤の含有量は、その添加目的に応じて適宜設定すればよい。
[Other additives]
The polishing composition of the present invention includes a chelating agent, a thickening agent, an oxidizing agent, a dispersing agent, a surface protecting agent, a wetting agent, and a surfactant having a Log P of less than 1.0 as long as the effects of the present invention are not impaired. Further, known additives such as a rust preventive, a preservative, and a fungicide may be further contained. What is necessary is just to set the content of the said additive suitably according to the addition purpose.
本発明の研磨用組成物は、酸化剤を実質的に含有しないことが好ましい。ここでいう酸化剤の具体例としては、過酸化水素（Ｈ２Ｏ２）、過硫酸ナトリウム、過硫酸アンモニウム、ジクロロイソシアヌル酸ナトリウム等が挙げられる。なお、「研磨用組成物が酸化剤を実質的に含有しない」とは、少なくとも意図的には酸化剤を含有させないことをいう。したがって、原料や製法等に由来して微量の酸化剤が不可避的に含まれている研磨用組成物は、ここでいう酸化剤を実質的に含有しない研磨用組成物の概念に包含され得る。たとえば、研磨用組成物中における酸化剤のモル濃度が０．０００５モル／Ｌ以下、好ましくは０．０００１モル／Ｌ以下、より好ましくは０．００００１モル／Ｌ以下、特に好ましくは０．０００００１モル／Ｌ以下である。 It is preferable that the polishing composition of the present invention does not substantially contain an oxidizing agent. Specific examples of the oxidizing agent mentioned here include hydrogen peroxide (H 2 O 2 ), sodium persulfate, ammonium persulfate, sodium dichloroisocyanurate, and the like. Here, "the polishing composition does not substantially contain an oxidizing agent" means that the oxidizing agent is not intentionally contained at least intentionally. Therefore, a polishing composition in which a trace amount of an oxidizing agent is inevitably contained due to a raw material, a production method, or the like can be included in the concept of the polishing composition substantially containing no oxidizing agent. For example, the molar concentration of the oxidizing agent in the polishing composition is 0.0005 mol / L or less, preferably 0.0001 mol / L or less, more preferably 0.00001 mol / L or less, and particularly preferably 0.000001 mol / L. / L or less.
＜研磨用組成物の製造方法＞
本発明の研磨用組成物の製造方法は、特に制限されず、たとえば、砥粒、ＬｏｇＰが１．０以上である化合物、および必要に応じて他の添加剤を、分散媒中で攪拌混合することにより得ることができる。各成分の詳細は上述した通りである。したがって、本発明は、酸化ケイ素膜を含む研磨対象物を研磨するために用いられ、ｐＨが７未満である研磨用組成物の製造方法であって、砥粒と、ＬｏｇＰが１．０以上である化合物と、分散媒と、を混合することを有する、研磨用組成物の製造方法を提供する。
<Method for producing polishing composition>
The method for producing the polishing composition of the present invention is not particularly limited. For example, abrasive grains, a compound having a LogP of 1.0 or more, and other additives as necessary are stirred and mixed in a dispersion medium. Can be obtained. Details of each component are as described above. Therefore, the present invention is a method for producing a polishing composition which is used for polishing a polishing object including a silicon oxide film and has a pH of less than 7, wherein the abrasive grains and LogP are 1.0 or more. Provided is a method for producing a polishing composition, comprising mixing a certain compound and a dispersion medium.
各成分を混合する際の温度は特に制限されないが、１０℃以上４０℃以下が好ましく、溶解速度を上げるために加熱してもよい。また、混合時間も、均一混合できれば特に制限されない。 The temperature at which the components are mixed is not particularly limited, but is preferably from 10 ° C to 40 ° C, and heating may be performed to increase the dissolution rate. The mixing time is not particularly limited as long as the mixing can be performed uniformly.
＜研磨方法および半導体基板の製造方法＞
上述のように、本発明の研磨用組成物は、酸化ケイ素膜を含む研磨対象物の研磨に好適に用いられる。よって、本発明は、酸化ケイ素膜を含む研磨対象物を準備する工程と、本発明の研磨用組成物を用いて前記研磨対象物を研磨する工程と、を含む研磨方法を提供する。また、本発明は、酸化ケイ素膜を含む半導体基板を上記研磨方法で研磨する工程を含む、半導体基板の製造方法を提供する。
<Polishing method and semiconductor substrate manufacturing method>
As described above, the polishing composition of the present invention is suitably used for polishing an object to be polished including a silicon oxide film. Therefore, the present invention provides a polishing method including a step of preparing a polishing target including a silicon oxide film and a step of polishing the polishing target using the polishing composition of the present invention. Further, the present invention provides a method for manufacturing a semiconductor substrate, which includes a step of polishing a semiconductor substrate including a silicon oxide film by the above polishing method.
研磨装置としては、研磨対象物を有する基板等を保持するホルダーと回転数を変更可能なモータ等とが取り付けてあり、研磨パッド（研磨布）を貼り付け可能な研磨定盤を有する一般的な研磨装置を使用することができる。 As a polishing apparatus, a holder for holding a substrate or the like having an object to be polished, a motor or the like capable of changing the number of rotations, and the like are attached. A polishing device can be used.
研磨パッドとしては、一般的な不織布、ポリウレタン、および多孔質フッ素樹脂等を特に制限なく使用することができる。研磨パッドには、研磨液が溜まるような溝加工が施されていることが好ましい。 As the polishing pad, general nonwoven fabric, polyurethane, porous fluororesin, or the like can be used without particular limitation. The polishing pad is preferably provided with a groove processing for retaining the polishing liquid.
研磨条件については、たとえば、研磨定盤の回転速度は、１０ｒｐｍ（０．１７ｓ−１）以上５００ｒｐｍ（８．３ｓ−１）が好ましい。研磨対象物を有する基板にかける圧力（研磨圧力）は、０．５ｐｓｉ（３．４ｋＰａ）以上１０ｐｓｉ（６８．９ｋＰａ）以下が好ましい。研磨パッドに研磨用組成物を供給する方法も特に制限されず、たとえば、ポンプ等で連続的に供給する方法が採用される。この供給量に制限はないが、研磨パッドの表面が常に本発明の研磨用組成物で覆われていることが好ましい。 Regarding the polishing conditions, for example, the rotation speed of the polishing platen is preferably 10 rpm (0.17 s -1 ) or more and 500 rpm (8.3 s -1 ). The pressure (polishing pressure) applied to the substrate having the object to be polished is preferably 0.5 psi (3.4 kPa) or more and 10 psi (68.9 kPa) or less. The method for supplying the polishing composition to the polishing pad is not particularly limited, either. For example, a method for continuously supplying the composition with a pump or the like is employed. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the polishing composition of the present invention.
研磨終了後、基板を流水中で洗浄し、スピンドライヤ等により基板上に付着した水滴を払い落として乾燥させることにより、金属を含む層を有する基板が得られる。 After the polishing, the substrate is washed in running water, and water droplets attached to the substrate are removed by a spin drier or the like and dried to obtain a substrate having a metal-containing layer.
本発明の研磨用組成物は一液型であってもよいし、二液型をはじめとする多液型であってもよい。また、本発明の研磨用組成物は、研磨用組成物の原液を水などの希釈液を使って、たとえば１０倍以上に希釈することによって調製されてもよい。 The polishing composition of the present invention may be a one-part type or a two-part type or other multi-part type. Further, the polishing composition of the present invention may be prepared by diluting a stock solution of the polishing composition with a diluent such as water, for example, at least 10 times.
＜研磨システム＞
本発明は、酸化ケイ素膜を含む研磨対象物、研磨パッド、および研磨用組成物を含む研磨システムであって、前記研磨用組成物は、砥粒と、ＬｏｇＰが１．０以上である化合物と、分散媒と、を含み、前記研磨対象物の表面を前記研磨パッドおよび前記研磨用組成物と接触させる、研磨システムを提供する。
<Polishing system>
The present invention is a polishing object including a polishing object including a silicon oxide film, a polishing pad, and a polishing composition, wherein the polishing composition comprises an abrasive, a compound having a LogP of 1.0 or more. And a dispersion medium, wherein the surface of the object to be polished is brought into contact with the polishing pad and the polishing composition.
本発明の研磨システムに適用される研磨対象物および研磨用組成物については、上記と同様であるため、ここでは説明を省略する。 The object to be polished and the polishing composition applied to the polishing system of the present invention are the same as those described above, and thus description thereof is omitted here.
本発明の研磨システムに使用される研磨パッドは、特に制限されず、たとえば、発泡ポリウレタンタイプ、不織布タイプ、スウェードタイプ、砥粒を含むもの、砥粒を含まないもの等を使用することができる。 The polishing pad used in the polishing system of the present invention is not particularly limited, and for example, a foamed polyurethane type, a nonwoven fabric type, a suede type, one containing abrasive grains, one containing no abrasive grains, and the like can be used.
本発明の研磨システムは、研磨対象物の両面を研磨パッドおよび研磨用組成物と接触させて、研磨対象物の両面を同時に研磨するものであってもよいし、研磨対象物の片面のみを研磨パッドおよび研磨用組成物と接触させて、研磨対象物の片面のみを研磨するものであってもよい。 The polishing system of the present invention may be one in which both surfaces of the object to be polished are brought into contact with a polishing pad and a polishing composition to simultaneously polish both surfaces of the object to be polished, or only one surface of the object to be polished is polished. It may be one in which only one surface of the object to be polished is brought into contact with the pad and the polishing composition.
本発明の研磨システムでは、上記の研磨用組成物を含むワーキングスラリーを用意する。次いで、その研磨用組成物を研磨対象物に供給し、常法により研磨する。たとえば、一般的な研磨装置に研磨対象物をセットし、該研磨装置の研磨パッドを通じて該研磨対象物の表面（研磨対象面）に研磨用組成物を供給する。典型的には、上記研磨用組成物を連続的に供給しつつ、研磨対象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（たとえば回転移動）させる。かかる研磨工程を経て研磨対象物の研磨が完了する。 In the polishing system of the present invention, a working slurry containing the above polishing composition is prepared. Next, the polishing composition is supplied to an object to be polished and polished by a conventional method. For example, an object to be polished is set in a general polishing apparatus, and a polishing composition is supplied to a surface of the object to be polished (a surface to be polished) through a polishing pad of the polishing apparatus. Typically, while continuously supplying the polishing composition, the polishing pad is pressed against the surface of the object to be polished, and the two are relatively moved (for example, rotated). Through such a polishing step, polishing of the object to be polished is completed.
研磨条件については、たとえば、研磨定盤の回転速度は、１０ｒｐｍ（０．１７ｓ−１）以上５００ｒｐｍ（８．３ｓ−１）以下が好ましい。研磨対象物を有する基板にかける圧力（研磨圧力）は、０．５ｐｓｉ（３．４ｋＰａ）以上１０ｐｓｉ（６８．９ｋＰａ）以下が好ましい。研磨パッドに研磨用組成物を供給する方法も特に制限されず、たとえば、ポンプ等で連続的に供給する方法が採用される。この供給量に制限はないが、研磨パッドの表面が常に本発明の研磨用組成物で覆われていることが好ましい。 Regarding the polishing conditions, for example, the rotation speed of the polishing platen is preferably 10 rpm (0.17 s -1 ) or more and 500 rpm (8.3 s -1 ) or less. The pressure (polishing pressure) applied to the substrate having the object to be polished is preferably 0.5 psi (3.4 kPa) or more and 10 psi (68.9 kPa) or less. The method for supplying the polishing composition to the polishing pad is not particularly limited, either. For example, a method for continuously supplying the composition with a pump or the like is employed. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the polishing composition of the present invention.
本発明を、以下の実施例および比較例を用いてさらに詳細に説明する。ただし、本発明の技術的範囲が以下の実施例のみに制限されるわけではない。なお、特記しない限り、「％」および「部」は、それぞれ、「質量％」および「質量部」を意味する。また、下記実施例において、特記しない限り、操作は室温（２０℃以上２５℃以下）／相対湿度４０％ＲＨ以上５０％ＲＨ以下の条件下で行われた。 The present invention will be described in more detail with reference to the following Examples and Comparative Examples. However, the technical scope of the present invention is not limited only to the following examples. Unless otherwise specified, “%” and “parts” mean “% by mass” and “parts by mass”, respectively. In the following examples, unless otherwise specified, the operation was performed under the conditions of room temperature (20 ° C. or more and 25 ° C. or less) / relative humidity of 40% RH or more and 50% RH or less.
＜研磨用組成物の調製＞
（実施例１）
砥粒としてカチオン変性コロイダルシリカ（平均一次粒子径３１ｎｍ、平均二次粒子径６２ｎｍ、平均会合度２．０）を、研磨用組成物の総質量を１００質量％として１．５質量％の濃度となるように水に加えた。さらに、酢酸を０．１５ｇ／Ｌの濃度となるように、酢酸アンモニウムを０．０６ｇ／Ｌの濃度となるように、オレイン酸ジエタノールアミドを１００質量ｐｐｍの濃度となるように、それぞれ添加した。その後、室温（２５℃）で３０分攪拌混合し、研磨用組成物を調製した。得られた研磨用組成物のｐＨは、４．５であった。
<Preparation of polishing composition>
(Example 1)
Cation-modified colloidal silica (average primary particle diameter 31 nm, average secondary particle diameter 62 nm, average degree of association 2.0) as abrasive grains, and a concentration of 1.5% by mass with the total mass of the polishing composition being 100% by mass. Was added to the water. Further, acetic acid was added at a concentration of 0.15 g / L, ammonium acetate was added at a concentration of 0.06 g / L, and diethanolamide oleate was added at a concentration of 100 mass ppm. Thereafter, the mixture was stirred and mixed at room temperature (25 ° C.) for 30 minutes to prepare a polishing composition. The pH of the obtained polishing composition was 4.5.
砥粒の平均一次粒子径は、マイクロメリティックス社製の“Ｆｌｏｗ Ｓｏｒｂ ＩＩ ２３００”を用いて測定されたＢＥＴ法による砥粒の比表面積と、砥粒の密度とから算出した。また、砥粒の平均二次粒子径は、日機装株式会社製 動的光散乱式粒子径・粒度分布装置 ＵＰＡ−ＵＴＩ１５１により測定した。さらに、研磨用組成物（液温：２５℃）のｐＨは、ｐＨメーター（株式会社 堀場製作所製 型番：ＬＡＱＵＡ）により確認した。 The average primary particle diameter of the abrasive grains was calculated from the specific surface area of the abrasive grains by the BET method measured using "Flow Sorb II 2300" manufactured by Micromeritics Co., Ltd., and the density of the abrasive grains. The average secondary particle diameter of the abrasive grains was measured by a dynamic light scattering particle size / particle size distribution analyzer UPA-UTI151 manufactured by Nikkiso Co., Ltd. Further, the pH of the polishing composition (liquid temperature: 25 ° C.) was confirmed with a pH meter (model number: LAQUA manufactured by HORIBA, Ltd.).
（実施例２〜４、比較例１〜８）
スクラッチ低減剤の種類およびｐＨ調整剤の種類を下記表１のように変更したこと以外は、実施例１と同様にして、各研磨用組成物を調製した。
(Examples 2 to 4, Comparative Examples 1 to 8)
Each polishing composition was prepared in the same manner as in Example 1 except that the type of the scratch reducing agent and the type of the pH adjuster were changed as shown in Table 1 below.
［評価１］
研磨対象物として、２００ｍｍのＢＰＳＧ基板（アドバンスマテリアルズテクノロジー株式会社製）を準備した。上記で得られた実施例１〜４および比較例１〜８の各研磨用組成物を用いて、ＢＰＳＧ基板を以下の研磨条件で研磨した。
[Evaluation 1]
A 200-mm BPSG substrate (manufactured by Advanced Materials Technology Co., Ltd.) was prepared as an object to be polished. Using the polishing compositions of Examples 1 to 4 and Comparative Examples 1 to 8 obtained above, a BPSG substrate was polished under the following polishing conditions.
（研磨条件）
研磨機として、Ｍｉｒｒａ（アプライド マテリアル社製）、研磨パッドとしてＩＣ１０００（ロームアンドハース社製）、研磨パッドのコンディショナーとしてＡ１６５（３Ｍ社製）をそれぞれ用いた。研磨圧力４．０ｐｓｉ（２７．５９ｋＰａ）、定盤回転数１２３ｒｐｍ、ヘッド回転数１１７ｒｐｍ、研磨用組成物の供給速度１３０ｍｌ／ｍｉｎの条件で、研磨時間は６０秒で研磨を実施した。コンディショナーによるパッドコンディショニングは、研磨中に回転数１２０ｒｐｍ、圧力５ｌｂｆ（２２．２４Ｎ）、ｉｎ−ｓｉｔｕで行った。
(Polishing conditions)
Mirar (manufactured by Applied Materials) was used as the polishing machine, IC1000 (manufactured by Rohm and Haas) was used as the polishing pad, and A165 (manufactured by 3M) was used as the conditioner of the polishing pad. Polishing was performed at a polishing pressure of 4.0 psi (27.59 kPa), a platen rotation speed of 123 rpm, a head rotation speed of 117 rpm, and a supply speed of the polishing composition of 130 ml / min, for a polishing time of 60 seconds. The pad conditioning by the conditioner was performed during polishing at a rotation speed of 120 rpm, a pressure of 5 lbf (22.24 N), and in-situ.
＜スクラッチ数＞
研磨対象物表面のスクラッチ数は、ケーエルエー・テンコール社製のウェーハ検査装置“Ｓｕｒｆｓｃａｎ（登録商標）ＳＰ２”を用いて、ウェーハ全面（ただし外周２ｍｍは除く）の座標を測定し、測定した座標をＲｅｖｉｅｗ−ＳＥＭ（ＲＳ−６０００、株式会社日立ハイテクノロジーズ製）で全数観察することで、スクラッチ数を測定した。
<Number of scratches>
The number of scratches on the surface of the object to be polished can be determined by measuring the coordinates of the entire surface of the wafer (excluding the outer periphery of 2 mm) using a wafer inspection apparatus “Surfscan (registered trademark) SP2” manufactured by KLA Tencor Co., and reviewing the measured coordinates. -The number of scratches was measured by observing all the samples with a SEM (RS-6000, manufactured by Hitachi High-Technologies Corporation).
＜研磨レート＞
研磨レート（Ｒｅｍｏｖａｌ Ｒａｔｅ；ＲＲ、研磨速度）は、以下の式により計算した。
<Polishing rate>
The polishing rate (Removal Rate; RR, polishing rate) was calculated by the following equation.
膜厚は、光干渉式膜厚測定装置（ケーエルエー・テンコール（ＫＬＡ−Ｔｅｎｃｏｒ）株式会社製 型番：ＡＳＥＴ−ｆ５ｘ）によって求めて、研磨前後の膜厚の差を研磨時間で除することにより研磨レートを評価した。 The film thickness is obtained by an optical interference type film thickness measuring device (manufactured by KLA-Tencor Co., Ltd., model number: ASET-f5x), and the polishing rate is obtained by dividing the difference in film thickness before and after polishing by the polishing time. Was evaluated.
スクラッチ数および研磨レートの評価結果を下記表１に示す。 Table 1 shows the evaluation results of the number of scratches and the polishing rate.
上記表１から明らかなように、ＬｏｇＰが１．０以上であるスクラッチ低減剤を含む実施例の研磨用組成物を用いた場合、比較例１〜８の研磨用組成物と比べて、ＢＰＳＧ膜を含む研磨対象物を高い研磨速度で研磨でき、かつＢＰＳＧ膜を含む研磨対象物表面のスクラッチを十分に低減できることがわかった。一方、比較例１〜８の研磨用組成物を用いた場合、ＢＰＳＧ膜を含む研磨対象物表面のスクラッチの低減が不十分であり、また、比較例７〜８の研磨用組成物を用いた場合、研磨速度が低いことがわかった。 As is clear from Table 1 above, when the polishing composition of the example including the scratch reducing agent having LogP of 1.0 or more was used, the BPSG film was compared with the polishing compositions of Comparative Examples 1 to 8. It has been found that the polishing target containing, can be polished at a high polishing rate, and the scratch on the surface of the polishing target including the BPSG film can be sufficiently reduced. On the other hand, when the polishing compositions of Comparative Examples 1 to 8 were used, the reduction of the scratches on the surface of the polishing target including the BPSG film was insufficient, and the polishing compositions of Comparative Examples 7 and 8 were used. In this case, it was found that the polishing rate was low.
（実施例５）
砥粒として未変性コロイダルシリカ（平均一次粒子径３１ｎｍ、平均二次粒子径６２ｎｍ、平均会合度２．０）を、研磨用組成物の総質量を１００質量％として０．５質量％の濃度となるように水に加えた。さらに、エチドロン酸（ＨＥＤＰ）を０．７５ｇ／Ｌの濃度となるように、オレイン酸ジエタノールアミドを１００質量ｐｐｍの濃度となるように、それぞれ添加した。その後、室温（２５℃）で３０分攪拌混合し、研磨用組成物を調製した。得られた研磨用組成物のｐＨは、２．５であった。
(Example 5)
Unmodified colloidal silica (average primary particle diameter 31 nm, average secondary particle diameter 62 nm, average degree of association 2.0) as abrasive grains, and a concentration of 0.5% by mass with the total mass of the polishing composition being 100% by mass. Was added to the water. Further, etidronic acid (HEDP) was added to a concentration of 0.75 g / L, and diethanolamide oleate was added to a concentration of 100 mass ppm. Thereafter, the mixture was stirred and mixed at room temperature (25 ° C.) for 30 minutes to prepare a polishing composition. The pH of the obtained polishing composition was 2.5.
（実施例６〜７、比較例９）
ｐＨ調整剤の量およびスクラッチ低減剤の種類を下記表２のように変更したこと以外は、実施例５と同様にして、各研磨用組成物を調製した。
(Examples 6 and 7, Comparative Example 9)
Each polishing composition was prepared in the same manner as in Example 5, except that the amount of the pH adjuster and the type of the scratch reducing agent were changed as shown in Table 2 below.
［評価２］
研磨対象物として、３００ｍｍのＴＥＯＳ基板（アドバンテック株式会社製）を準備した。上記で得られた実施例５〜７および比較例９の各研磨用組成物を用いて、ＴＥＯＳ基板を上記評価１と同様の研磨条件で研磨した。その後、上記評価１と同様の方法で、スクラッチ数および研磨レートを評価した。結果を下記表２に示す。
[Evaluation 2]
A 300 mm TEOS substrate (manufactured by Advantech Co., Ltd.) was prepared as an object to be polished. Using each of the polishing compositions of Examples 5 to 7 and Comparative Example 9 obtained above, a TEOS substrate was polished under the same polishing conditions as in Evaluation 1 described above. Thereafter, the number of scratches and the polishing rate were evaluated in the same manner as in Evaluation 1 described above. The results are shown in Table 2 below.
上記表２から明らかなように、ＬｏｇＰが１．０以上であるスクラッチ低減剤を含む実施例５〜７の研磨用組成物を用いた場合、比較例９の研磨用組成物と比べて、ＴＥＯＳ膜を含む研磨対象物を高い研磨速度で研磨でき、かつＴＥＯＳ膜を含む研磨対象物表面のスクラッチを十分に低減できることがわかった。一方、比較例９の研磨用組成物を用いた場合、ＴＥＯＳ膜を含む研磨対象物表面のスクラッチの低減が不十分であり、研磨速度も低いことがわかった。 As is clear from Table 2 above, when the polishing compositions of Examples 5 to 7 containing the scratch reducing agent having LogP of 1.0 or more were used, the TEOS was lower than that of Comparative Example 9. It has been found that the polishing target including the film can be polished at a high polishing rate and the scratch on the surface of the polishing target including the TEOS film can be sufficiently reduced. On the other hand, when the polishing composition of Comparative Example 9 was used, it was found that the reduction of scratches on the surface of the object to be polished including the TEOS film was insufficient, and the polishing rate was low.
Claims (13)
砥粒と、分配係数の対数値（ＬｏｇＰ）が１．０以上である化合物と、分散媒と、を含有し、
ｐＨが７．０未満である、研磨用組成物。 A polishing composition used for polishing a polishing object including a silicon oxide film,
Containing an abrasive, a compound having a logarithmic value of distribution coefficient (LogP) of 1.0 or more, and a dispersion medium,
A polishing composition having a pH of less than 7.0.
砥粒と、分配係数の対数値（ＬｏｇＰ）が１．０以上である化合物と、分散媒と、を混合することを有する、研磨用組成物の製造方法。 A method for producing a polishing composition having a pH of less than 7.0, which is used for polishing an object to be polished including a silicon oxide film,
A method for producing a polishing composition, comprising mixing abrasive particles, a compound having a logarithmic value (LogP) of 1.0 or more of a distribution coefficient, and a dispersion medium.
請求項１〜９のいずれか１項に記載の研磨用組成物を用いて、前記研磨対象物の表面を研磨する工程と、
を有する、研磨方法。 A step of preparing a polishing object including a silicon oxide film,
Polishing the surface of the object to be polished, using the polishing composition according to any one of claims 1 to 9,
A polishing method comprising:
前記研磨用組成物は、砥粒と、分配係数の対数値（ＬｏｇＰ）が１．０以上である化合物と、分散媒と、を含有し、かつｐＨが７．０未満であり、
前記研磨対象物の表面を前記研磨パッドおよび前記研磨用組成物と接触させる、研磨システム。 A polishing object including a silicon oxide film, a polishing pad, and a polishing system including a polishing composition,
The polishing composition contains abrasive grains, a compound having a logarithmic value of distribution coefficient (LogP) of 1.0 or more, and a dispersion medium, and has a pH of less than 7.0,
A polishing system for bringing a surface of the polishing object into contact with the polishing pad and the polishing composition.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW108126304A TWI828727B (en) | 2018-09-04 | 2019-07-25 | Grinding compositions and grinding systems |
| US16/557,271 US20200071567A1 (en) | 2018-09-04 | 2019-08-30 | Polishing composition and polishing system |
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| KR20210143543A (en) * | 2020-05-20 | 2021-11-29 | 삼성에스디아이 주식회사 | Cmp slurry composition for polishing tungsten and method for polishing tungsten using the same |
| KR20240044340A (en) | 2022-09-28 | 2024-04-04 | 가부시키가이샤 후지미인코퍼레이티드 | Polishing composition, method for producing polishing composition, polishing method, method for producing semiconductor substrate |
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| TWI828727B (en) | 2024-01-11 |
| JP7316797B2 (en) | 2023-07-28 |
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