JP2007242839A - Abrasive compound for metal chemical mechanical polishing - Google Patents
Abrasive compound for metal chemical mechanical polishing Download PDFInfo
- Publication number
- JP2007242839A JP2007242839A JP2006062303A JP2006062303A JP2007242839A JP 2007242839 A JP2007242839 A JP 2007242839A JP 2006062303 A JP2006062303 A JP 2006062303A JP 2006062303 A JP2006062303 A JP 2006062303A JP 2007242839 A JP2007242839 A JP 2007242839A
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- JP
- Japan
- Prior art keywords
- acid
- polishing
- polishing composition
- metal cmp
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000005498 polishing Methods 0.000 title claims abstract description 122
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 76
- 239000002184 metal Substances 0.000 title claims abstract description 76
- 150000001875 compounds Chemical class 0.000 title claims abstract description 27
- 239000000126 substance Substances 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 84
- 239000006061 abrasive grain Substances 0.000 claims description 19
- 229920003169 water-soluble polymer Polymers 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 239000008119 colloidal silica Substances 0.000 claims description 8
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 34
- 239000010949 copper Substances 0.000 abstract description 34
- -1 anticorrosives Substances 0.000 description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 33
- 230000000694 effects Effects 0.000 description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 150000003863 ammonium salts Chemical class 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 229910000881 Cu alloy Inorganic materials 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 7
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
本発明は、金属ＣＭＰ（Chemical Mechanical Polishing、化学機械研磨）用研磨組成物に関するものであり、特に半導体装置の製造に当たってダマシン法により配線を形成する際に、銅、銅合金層の除去に好ましく使用される金属ＣＭＰ用研磨組成物に関するものである。 TECHNICAL FIELD The present invention relates to a polishing composition for metal CMP (Chemical Mechanical Polishing), and preferably used for removing copper and copper alloy layers when forming wiring by a damascene method particularly in the manufacture of semiconductor devices. The present invention relates to a polishing composition for metal CMP.
半導体装置の製造に当たりダマシン法により配線を形成する際には、剰余の銅または銅合金層およびバリアメタル層の除去にＣＭＰ研磨が行われている。このＣＭＰ研磨においてよく行われる２段研磨法では、第１段研磨で最表層部の銅または銅合金層のみを、配線部銅または銅合金層のディッシングをタンタル系バリア層の厚みより小さく抑えつつ選択的に研磨し、第２段研磨では最表層部銅または銅合金層の研磨後露出したタンタル系バリア層のみを、絶縁膜および配線部銅または銅合金層のエロージョンを抑制しながら選択的に研磨することが望まれている。これに加えて最近では、金属表面の表面状態や平坦性についても良好であることも求められている。 When a wiring is formed by a damascene method in manufacturing a semiconductor device, CMP polishing is performed to remove excess copper or copper alloy layer and barrier metal layer. In the two-step polishing method often used in this CMP polishing, only the outermost layer copper or copper alloy layer is reduced in the first step polishing while the dishing of the wiring portion copper or copper alloy layer is suppressed to be smaller than the thickness of the tantalum-based barrier layer. Selectively polished, and in the second stage polishing, only the tantalum-based barrier layer exposed after polishing the outermost layer copper or copper alloy layer is selectively suppressed while suppressing the erosion of the insulating film and the wiring portion copper or copper alloy layer. It is desired to polish. In addition to this, recently, the surface state and flatness of the metal surface are also required to be good.
ＣＭＰ技術は、回転する板の上に平坦化処理を行うウエハを載せ、ウエハ表面にパッドを接触させ、ウエハとパッド間に研磨スラリを供給しながら回転盤とパッドを両方とも回転させて研磨を行う。スラリ内の研磨粒子とパッド表面の機械的作用でウエハ表面が研磨されると同時に、スラリ内の化合物とウエハ表面の化学反応によりウエハ表面が平坦化される。 In CMP technology, a wafer to be planarized is placed on a rotating plate, a pad is brought into contact with the wafer surface, and polishing is performed by rotating both the rotating disk and the pad while supplying a polishing slurry between the wafer and the pad. Do. The wafer surface is polished by the mechanical action of the abrasive particles in the slurry and the pad surface, and at the same time, the wafer surface is flattened by a chemical reaction between the compound in the slurry and the wafer surface.
ＣＭＰに用いることのできる研磨組成物の成分としては、研磨砥粒、金属酸化剤、金属溶解剤、防食剤、活性剤、水溶性高分子化合物などが提案されている。 As components of a polishing composition that can be used in CMP, polishing abrasive grains, metal oxidizers, metal solubilizers, anticorrosives, activators, water-soluble polymer compounds, and the like have been proposed.
例えば、特許文献１は、複素環を有する化合物、界面活性剤、金属酸化剤、研磨砥粒、有機酸およびｐＨ調整剤を含有するＣＭＰ用研磨組成物を開示している。上記複素環を有する化合物としてベンゾトリアゾールなどが例示されており、上記界面活性剤としてドデシルベンゼンスルホン酸またはその塩が例示されており、上記金属酸化剤として過酸化水素、過硫酸アンモニウム、硝酸セリウムアンモニウム、過ヨウ素酸カリウム、過ヨウ素酸塩およびオゾン水が例示されており、上記研磨砥粒としてコロイダルシリカが例示されており、上記有機酸としてギ酸、酢酸およびシュウ酸などが例示されており、上記ｐＨ調整剤として、水酸化カリウムおよび水酸化ナトリウムなどの無機アルカリ化合物およびアンモニアが例示されている。 For example, Patent Document 1 discloses a polishing composition for CMP containing a compound having a heterocyclic ring, a surfactant, a metal oxidizing agent, polishing abrasive grains, an organic acid, and a pH adjuster. Examples of the compound having a heterocyclic ring include benzotriazole, and examples of the surfactant include dodecylbenzenesulfonic acid or a salt thereof. Examples of the metal oxidizing agent include hydrogen peroxide, ammonium persulfate, cerium ammonium nitrate, Examples are potassium periodate, periodate and ozone water, colloidal silica is exemplified as the abrasive grains, formic acid, acetic acid and oxalic acid are exemplified as the organic acid, and the pH Examples of the regulator include inorganic alkali compounds such as potassium hydroxide and sodium hydroxide and ammonia.
また、特許文献２は、金属酸化剤、酸化金属溶解剤、金属防食剤、銅或いは銅合金の電位を低下させることのできる化合物、研磨砥粒および水溶性ポリマーを含有するＣＭＰ用研磨組成物を開示している。上記金属酸化剤として過酸化水素、硝酸、過ヨウ素酸カリウム、次亜塩素酸塩、過硫酸塩およびオゾン水が例示されており、上記酸化金属溶解剤としてギ酸、酢酸、シュウ酸、リンゴ酸、クエン酸、およびこれらの有機酸のアンモニウム塩などが例示されており、上記金属防食剤としてトリアゾール類およびピリミジン類が例示されており、上記銅或いは銅合金の電位を低下させることのできる化合物としてドデシルベンゼンスルホン酸およびその塩などのアルキルベンゼン化合物が例示されている。上記研磨砥粒としてコロイダルシリカが例示されており、上記水溶性ポリマーとしてポリビニルピロリドンが例示されている。 Patent Document 2 discloses a polishing composition for CMP containing a metal oxidizer, a metal oxide solubilizer, a metal anticorrosive, a compound capable of lowering the potential of copper or a copper alloy, abrasive grains and a water-soluble polymer. Disclosure. Examples of the metal oxidant include hydrogen peroxide, nitric acid, potassium periodate, hypochlorite, persulfate, and ozone water. Examples of the metal oxide solubilizer include formic acid, acetic acid, oxalic acid, malic acid, Citric acid and ammonium salts of these organic acids are exemplified, and triazoles and pyrimidines are exemplified as the metal anticorrosive, and dodecyl is a compound capable of lowering the potential of the copper or copper alloy. Illustrative are alkylbenzene compounds such as benzenesulfonic acid and its salts. Colloidal silica is exemplified as the abrasive grains, and polyvinyl pyrrolidone is exemplified as the water-soluble polymer.
また、特許文献３は、芳香族スルホン酸およびその塩から選ばれる少なくとも１種と、芳香族カルボン酸およびその塩から選ばれる少なくとも１種、研磨砥粒、金属酸化剤、金属防食剤および水溶性ポリマーを含有する研磨液を開示している。上記芳香族スルホン酸として、１−ナフタレンスルホン酸が記載されており、上記研磨砥粒としてはコロイダルシリカが例示されており、上記金属酸化剤としては、過酸化水素、硝酸、過ヨウ素酸カリウム、次亜塩素酸およびオゾンが例示されており、上記金属防食剤としてベンゾトリアゾール類およびピリミジン類が例示されており、上記水溶性ポリマーとしてポリビニルピロリドンが例示されている。 Patent Document 3 discloses at least one selected from aromatic sulfonic acids and salts thereof, at least one selected from aromatic carboxylic acids and salts thereof, abrasive grains, metal oxidizers, metal anticorrosives, and water-solubility. A polishing liquid containing a polymer is disclosed. 1-naphthalenesulfonic acid is described as the aromatic sulfonic acid, colloidal silica is exemplified as the abrasive grain, and the metal oxidant includes hydrogen peroxide, nitric acid, potassium periodate, Hypochlorous acid and ozone are exemplified, benzotriazoles and pyrimidines are exemplified as the metal anticorrosive, and polyvinylpyrrolidone is exemplified as the water-soluble polymer.
金属ＣＭＰ用研磨組成物は、上記のような種々の成分の選択および配合の組み合わせにより、要求特性を満たすよう設計されているが、種々の要求性能について未だ改善の余地がある。特に銅はエッチングされやすく、研磨速度および研磨選択性などの研磨能力と平坦性および表面状態などの研磨後の形状とのバランスが得られにくい。例えば、ベンゾトリアゾールに代表される防食剤を使用して銅の過剰なエッチングによる弊害を抑えているが、研磨速度についてその効果は必ずしも満足できるものではなかった。従来の防食剤は、研磨圧力が小さいと研磨速度が大きく損なわれるという問題点を有している。 The polishing composition for metal CMP is designed to satisfy the required characteristics by the combination of selection and blending of the various components as described above, but there is still room for improvement in various required performances. In particular, copper is easily etched, and it is difficult to obtain a balance between polishing ability such as polishing rate and polishing selectivity and shape after polishing such as flatness and surface condition. For example, an anticorrosive agent typified by benzotriazole is used to suppress adverse effects caused by excessive etching of copper, but the effect on the polishing rate is not always satisfactory. Conventional anticorrosives have the problem that the polishing rate is greatly impaired when the polishing pressure is low.
本発明においては、金属ＣＭＰ、特に銅ＣＭＰによる研磨後の金属表面において良好な平坦性と良好な表面状態を与えるＣＭＰ用研磨組成物であり、充分な銅の研磨速度を有するプロセスマージンが大きい銅ＣＭＰ用研磨組成物を提供することを課題とする。 In the present invention, a polishing composition for CMP which gives good flatness and a good surface state on a metal surface after polishing by metal CMP, particularly copper CMP, and has a sufficient copper polishing rate and a large process margin. It is an object to provide a polishing composition for CMP.
本発明者などは、上記課題を解決するため鋭意研究の結果、特定の化合物を防食剤として用いた組成物が上記課題の解決に有効であることを知見し、本発明に到達した。すなわち、本発明は、下記一般式（１）で表される化合物を組成物全量の０．０００１〜１質量％になる割合で含有してなることを特徴とする金属ＣＭＰ用研磨組成物を提供する。
なお、以下の説明における各成分の含有量は、組成物全量を１００質量％としたときに、該組成物中に含まれる質量％（すなわち、内％）を意味している。
As a result of intensive studies to solve the above problems, the present inventors have found that a composition using a specific compound as an anticorrosive is effective in solving the above problems, and have reached the present invention. That is, this invention provides the polishing composition for metal CMP characterized by including the compound represented by following General formula (1) in the ratio used as 0.0001-1 mass% of the composition whole quantity. To do.
In addition, content of each component in the following description means the mass% (namely, inner%) contained in this composition, when a composition whole quantity shall be 100 mass%.
本発明によれば、半導体装置の製造に当たって、特にダマシン法により銅配線を形成する際に、研磨後の平坦性および表面状態が良好であり、銅層に対する充分な研磨速度を有する銅層の除去に好ましく使用できる金属ＣＭＰ用研磨組成物を提供することができる。 According to the present invention, in manufacturing a semiconductor device, particularly when forming a copper wiring by a damascene method, the flatness and surface state after polishing are good, and the removal of the copper layer having a sufficient polishing rate with respect to the copper layer. It is possible to provide a polishing composition for metal CMP that can be preferably used for the above.
上記一般式（１）で表される化合物は、本発明の金属ＣＭＰ用研磨組成物の必須成分であり、銅の過剰エッチングを防止する防食剤として機能するものである。上記一般式（１）で表される化合物の具体例としては、下記化合物Ｎｏ．１〜９が挙げられる。なお、上記一般式（１）で表される化合物は常法に従って合成することができるし、また、市場からチアベンダゾールなどの商品名で入手して使用することもできる。 The compound represented by the general formula (1) is an essential component of the polishing composition for metal CMP of the present invention and functions as an anticorrosive agent for preventing excessive etching of copper. Specific examples of the compound represented by the general formula (1) include the following compound No. 1-9 are mentioned. The compound represented by the general formula (1) can be synthesized according to a conventional method, or can be obtained from the market under a trade name such as thiabendazole.
上記化合物の中でも、前記一般式（１）においてＸがＮＨである化合物Ｎｏ．１〜３が、銅との親和性が適度であり、プロセス条件の変化に対して安定した防食効果を与えることができるので好ましく、前記一般式（１）においてＹがＳである化合物であるＮｏ．２が最も好ましい。 Among the above compounds, compound No. 1 wherein X is NH in the general formula (1). 1 to 3 are preferable because they have a moderate affinity with copper and can provide a stable anticorrosive effect against changes in process conditions, and are compounds in which Y is S in the general formula (1). . 2 is most preferred.
本発明の金属ＣＭＰ用研磨組成物中の上記一般式（１）で表される化合物の含有量は０．０００１〜１質量％である。含有量が上記下限より少ないと使用効果であるディッシングやエロージョンの抑制が難しくなり、一方、含有量が上記上限より多いと研磨速度が遅くなるという難点がある。含有量は０．０００５〜０．５質量％が好ましい。 Content of the compound represented by the said General formula (1) in the polishing composition for metal CMP of this invention is 0.0001-1 mass%. If the content is less than the above lower limit, it is difficult to suppress dishing and erosion, which are the effects of use, whereas if the content is more than the above upper limit, there is a disadvantage that the polishing rate is slowed. The content is preferably 0.0005 to 0.5 mass%.
本発明の金属ＣＭＰ用研磨組成物は、研磨砥粒成分を含有することが好ましい。含有される研磨砥粒としては、二酸化ケイ素、酸化アルミニウム、酸化セリウム、窒化ケイ素、酸化ジルコニウム、炭化ケイ素および二酸化マンガン、ポリスチレンおよびポリスチレンからなるラテックス、ポリアクリル酸およびポリアクリル酸エステルからなるラテックスなどが挙げられ、これらは１種類または２種類以上を混合して用いることができる。研磨砥粒としては、安定性などの面から非晶性二酸化ケイ素を用いることが好ましく、その中でもコロイダルシリカがより好ましい。 The metal CMP polishing composition of the present invention preferably contains a polishing abrasive grain component. The abrasive grains contained include silicon dioxide, aluminum oxide, cerium oxide, silicon nitride, zirconium oxide, silicon carbide and manganese dioxide, latex composed of polystyrene and polystyrene, latex composed of polyacrylic acid and polyacrylate ester, and the like. These can be used, and one kind or a mixture of two or more kinds can be used. As the abrasive grains, amorphous silicon dioxide is preferably used from the viewpoint of stability and the like, and among them, colloidal silica is more preferable.
コロイダルシリカには種々の粒径を持つ多くの種類があるが、本発明の金属ＣＭＰ用研磨組成物においてはその粒径が１〜４００ｎｍの範囲が好ましく、５〜２００ｎｍの範囲がより好ましい。本発明の金属ＣＭＰ用研磨組成物における研磨砥粒の含有量は、研磨面の平坦性を向上させる上から０．０１〜１０質量％が好ましい。含有量が上記下限より少ないと研磨速度が遅くなり、一方、含有量が上記上限より多いと、ディッシングの抑制が難しくなるという難点がある。研磨砥粒の含有量は０．０５〜５質量％の範囲がさらに好ましい。 There are many types of colloidal silica having various particle diameters. In the metal CMP polishing composition of the present invention, the particle diameter is preferably in the range of 1 to 400 nm, more preferably in the range of 5 to 200 nm. The content of the abrasive grains in the metal CMP polishing composition of the present invention is preferably 0.01 to 10% by mass from the viewpoint of improving the flatness of the polished surface. If the content is less than the above lower limit, the polishing rate becomes slow, while if the content is more than the above upper limit, it is difficult to suppress dishing. The content of the abrasive grains is more preferably in the range of 0.05 to 5% by mass.
本発明の金属ＣＭＰ用研磨組成物は、さらに有機酸成分を含有してもよい。含有される有機酸成分としては、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、グリコール酸、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、フマル酸、リンゴ酸、酒石酸、クエン酸および無水酢酸などの脂肪族カルボン酸；安息香酸、２−ヒドロキシ安息香酸、３−ヒドロキシ安息香酸、４−ヒドロキシ安息香酸、ｏ−フタル酸、ｍ−フタル酸、ｐ−フタル酸、キナルジン酸、ナフタレン−１−カルボン酸およびナフタレン−２−カルボン酸などの芳香族カルボン酸；メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、ブタンスルホン酸、ペンタンスルホン酸、ヘキサンスルホン酸、ヘプタンスルホン酸、オクタンスルホン酸、ノルボルネンスルホン酸、アダマンタンスルホン酸、シクロヘキサンスルホン酸、カンファースルホン酸、トリフルオロメタンスルホン酸、ペンタフルオロエタンスルホン酸およびヘプタフルオロプロパンスルホン酸などの脂肪族スルホン酸；ベンゼンスルホン酸、ｐ−トルエンスルホン酸、オクチルベンゼンスルホン酸、デシルベンゼンスルホン酸、ドデシルベンゼンスルホン酸、ナフタレン−１−スルホン酸、ナフタレン−２−スルホン酸、アントラセンスルホン酸、アセナフテンスルホン酸およびフェナントレンスルホン酸などの芳香族スルホン酸が挙げられ、これらは１種類または２種類以上の混合物で使用される。 The metal CMP polishing composition of the present invention may further contain an organic acid component. As the organic acid component contained, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n -Aliphatic carboxylic acids such as heptanoic acid, glycolic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid and acetic anhydride Benzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, quinaldic acid, naphthalene-1-carboxylic acid and naphthalene-2 -Aromatic carboxylic acids such as carboxylic acids; methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, pentane sulfone Aliphatic acids such as acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, norbornenesulfonic acid, adamantanesulfonic acid, cyclohexanesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid and heptafluoropropanesulfonic acid Sulfonic acid; benzenesulfonic acid, p-toluenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, anthracenesulfonic acid, acenaphthenesulfonic acid And aromatic sulfonic acids such as phenanthrenesulfonic acid, which are used in one or a mixture of two or more.
上記の有機酸成分の使用効果は、当該酸の化学構造により異なる。脂肪族カルボン酸および脂肪族スルホン酸は、銅ＣＭＰ用研磨組成物の安定性を高める効果があり、また、研磨速度を向上させる効果がある。芳香族カルボン酸および芳香族スルホン酸は銅の過剰エッチングなどを抑制し、研磨面の平坦化を良好にする効果がある。また、有機カルボン酸類は、研磨表面に残留物（マーキング）を与える場合があるので有機酸成分としては有機スルホン酸類が好ましい。 The effect of using the organic acid component is different depending on the chemical structure of the acid. Aliphatic carboxylic acid and aliphatic sulfonic acid have the effect of increasing the stability of the polishing composition for copper CMP, and also have the effect of increasing the polishing rate. Aromatic carboxylic acid and aromatic sulfonic acid have the effect of suppressing the excessive etching of copper and the like and improving the flatness of the polished surface. Moreover, since organic carboxylic acids may give a residue (marking) to the polishing surface, organic sulfonic acids are preferred as the organic acid component.
本発明の金属ＣＭＰ用研磨組成物中の有機酸成分の好ましい含有量は０．０００５〜５質量％である。含有量が上記下限より少ないと充分な使用効果が得られない場合があり、一方、含有量が上記上限より多いと使用効果が過剰となり、表面荒れ、平坦性悪化、研磨効率低下および選択研磨性の低下をきたす場合がある。 The preferred content of the organic acid component in the metal CMP polishing composition of the present invention is 0.0005 to 5 mass%. If the content is less than the above lower limit, a sufficient use effect may not be obtained. On the other hand, if the content is more than the above upper limit, the use effect becomes excessive, resulting in surface roughness, poor flatness, reduced polishing efficiency, and selective polishing properties. May decrease.
本発明の金属ＣＭＰ用研磨組成物の場合、好ましい有機酸成分は、芳香族スルホン酸である。例えば、ドデシルベンゼンスルホン酸およびナフタレン−２−スルホン酸は、研磨面の平坦性が優れるのでより好ましく配合され、この２種を併用するのがより好ましい。なお、ドデシルベンゼンスルホン酸は０．０２〜１質量％が好ましい配合量であり、ナフタレン−２−スルホン酸は０．０００５〜０．０５質量％が好ましい配合量である。 In the case of the metal CMP polishing composition of the present invention, a preferred organic acid component is an aromatic sulfonic acid. For example, dodecylbenzenesulfonic acid and naphthalene-2-sulfonic acid are more preferably blended because the flatness of the polished surface is excellent, and it is more preferable to use these two types in combination. In addition, 0.02-1 mass% is a preferable compounding quantity for dodecylbenzenesulfonic acid, and 0.0005-0.05 mass% is a preferable compounding quantity for naphthalene-2-sulfonic acid.
本発明の金属ＣＭＰ用研磨組成物は、水溶性高分子成分を含有してもよい。含有される水溶性高分子成分としては、例えば、アルギン酸、ペクチン酸、カルボキシメチルセルロース、寒天、カードランおよびプルランなどの多糖類；ポリアスパラギン酸、ポリグルタミン酸、ポリリシン、ポリリンゴ酸、ポリメタクリル酸、ポリアミド酸、ポリマレイン酸、ポリイタコン酸、ポリフマル酸、ポリ（ｐ−スチレンカルボン酸）、ポリアクリル酸、およびポリグリオキシル酸などのポリカルボン酸、ポリメタクリル酸アンモニウム塩、ポリメタクリル酸ナトリウム塩、ポリアクリルアミド、ポリアミノアクリルアミド、ポリアクリル酸アンモニウム塩、ポリアクリル酸ナトリウム塩、ポリアミド酸アンモニウム塩およびポリアミド酸ナトリウム塩などに例示されるポリカルボン酸の塩、エステルおよび誘導体；ポリビニルアルコール、ポリビニルピロリドンおよびポリアクロレインなどのビニル系ポリマー；ポリエチレングリコール、ポリプロピレングリコール、アルキレングリコールまたはポリアルキレングリコールのエチレンオキサイドおよびプロピレンオキサイドのランダムまたはブロック付加物などのポリアルキレングリコール類が挙げられ、これらは１種類または２種類以上の混合物で使用される。 The polishing composition for metal CMP of the present invention may contain a water-soluble polymer component. Examples of the water-soluble polymer component to be contained include polysaccharides such as alginic acid, pectic acid, carboxymethyl cellulose, agar, curdlan and pullulan; polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid, polyamic acid , Polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrene carboxylic acid), polyacrylic acid, polyglyoxylic acid and other polycarboxylic acids, polymethacrylic acid ammonium salt, polymethacrylic acid sodium salt, polyacrylamide, polyaminoacrylamide , Polycarboxylic acid salts, esters and derivatives exemplified by polyacrylic acid ammonium salt, polyacrylic acid sodium salt, polyamic acid ammonium salt and polyamic acid sodium salt; Vinyl-based polymers such as alcohol, polyvinyl pyrrolidone and polyacrolein; polyethylene glycol, polypropylene glycol, alkylene glycol or polyalkylene glycols such as random or block adducts of polyalkylene glycol ethylene oxide and propylene oxide, including 1 Used in one kind or a mixture of two or more kinds.
水溶性高分子成分の使用効果としては、バリア層研磨抑制による研磨選択性の向上、および研磨砥粒成分を用いた場合の研磨砥粒の分散安定化などが挙げられる。水溶性高分子成分の好ましい含有量は０．００１〜１０質量％である。含有量が上記下限より少ないと充分な使用効果が得られない場合があり、一方、含有量が上記上限より多いと充分な研磨速度を得ることができない場合がある。また、水溶性高分子成分の好ましい数平均分子量（ＧＰＣ測定、標準ポリスチレン換算）は種類により異なる。 Examples of the effects of using the water-soluble polymer component include improvement of polishing selectivity by suppressing barrier layer polishing, and dispersion stabilization of the abrasive grains when the abrasive abrasive grain component is used. The preferable content of the water-soluble polymer component is 0.001 to 10% by mass. If the content is less than the above lower limit, a sufficient use effect may not be obtained. On the other hand, if the content is more than the above upper limit, a sufficient polishing rate may not be obtained. Moreover, the preferable number average molecular weight (GPC measurement, standard polystyrene conversion) of a water-soluble polymer component changes with kinds.
本発明の金属ＣＭＰ用研磨組成物に含有される水溶性高分子成分として好適なもののひとつは、ポリビニルピロリドンである。ポリビニルピロリドンは、他の水溶性高分子成分と比較してバリア層研磨の抑制の効果が大きく銅の選択研磨性を向上させる利点を有する。また、砥粒の分散安定性を向上させる効果も大きい。本発明の金属ＣＭＰ用研磨組成物におけるポリビニルピロリドンの好ましい含有量は、バリア層の研磨抑制に効果が発現する０．００１〜５質量％である。また、ポリビニルピロリドンの数平均分子量としては５，０００〜１００，０００が好ましい。 One suitable water-soluble polymer component contained in the metal CMP polishing composition of the present invention is polyvinylpyrrolidone. Polyvinylpyrrolidone has an effect of suppressing the barrier layer polishing as compared with other water-soluble polymer components, and has an advantage of improving the selective polishing property of copper. Also, the effect of improving the dispersion stability of the abrasive grains is great. The preferable content of polyvinylpyrrolidone in the polishing composition for metal CMP of the present invention is 0.001 to 5% by mass, which is effective for suppressing the polishing of the barrier layer. The number average molecular weight of polyvinyl pyrrolidone is preferably 5,000 to 100,000.
また、本発明の金属ＣＭＰ用研磨組成物に含有される水溶性高分子成分として好適なもののひとつは、ポリアルキレングリコール類である。ポリアルキレングリコールは、他の水溶性高分子成分と比較して優れた研磨速度を示し、砥粒の分散安定性を向上させる効果も大きい。本発明の金属ＣＭＰ用研磨組成物におけるポリアルキレングリコール類の好ましい含有量は、バリア層の研磨抑制に効果が発現する０．００１〜５質量％である。また、ポリアルキレングリコールの数平均分子量としては２００〜３，０００が好ましい。 Also, one of the preferable water-soluble polymer components contained in the metal CMP polishing composition of the present invention is polyalkylene glycols. Polyalkylene glycol exhibits an excellent polishing rate as compared with other water-soluble polymer components, and has a large effect of improving the dispersion stability of abrasive grains. The preferable content of polyalkylene glycols in the polishing composition for metal CMP of the present invention is 0.001 to 5% by mass, which is effective for suppressing the polishing of the barrier layer. Further, the number average molecular weight of the polyalkylene glycol is preferably 200 to 3,000.
本発明の金属ＣＭＰ用研磨組成物のｐＨは、８〜１２が好ましい範囲である。ｐＨが８未満６以上であると、充分な研磨速度が得られない場合がある。また、６より小さいとバリア層の研磨が起こり、選択研磨性が低下する場合がある。また、ｐＨが１２より大きいとディッシングがおこり表面状態が悪化する場合がある。従って、本発明の金属ＣＭＰ用研磨組成物には、必要に応じてｐＨ調整剤成分を使用してもよい。 The pH of the polishing composition for metal CMP of the present invention is preferably in the range of 8-12. If the pH is less than 8 and 6 or more, a sufficient polishing rate may not be obtained. On the other hand, if it is smaller than 6, the barrier layer is polished, and the selective polishing property may be lowered. On the other hand, if the pH is greater than 12, dishing may occur and the surface state may deteriorate. Therefore, you may use a pH adjuster component for the metal CMP polishing composition of this invention as needed.
本発明の金属ＣＭＰ用研磨組成物に使用されるｐＨ調整剤成分は、水溶性塩基性化合物である。該化合物としては、水酸化リチウム、水酸化ナトリウムおよび水酸化カリウムなどの水酸化アルカリ金属類；水酸化カルシウム、水酸化ストロンチウムおよび水酸化バリウムなどの水酸化アルカリ土類金属類；炭酸アンモニウム、炭酸リチウム、炭酸ナトリウムおよび炭酸カリウムなどのアルカリ金属の炭酸塩類；テトラメチルアンモニウムヒドロキシドおよびコリンなどの４級アンモニウムヒドロキシド類；エチルアミン、ジエチルアミン、トリエチルアミンおよびヒドロキシエチルアミンなどの有機アミン類；アンモニアが挙げられ、これらは１種類または２種類以上の混合物で使用される。中でも安価で扱い易いので水酸化アルカリ金属類が好ましい。 The pH adjuster component used in the metal CMP polishing composition of the present invention is a water-soluble basic compound. Examples of the compound include alkali hydroxide metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkaline earth metals such as calcium hydroxide, strontium hydroxide and barium hydroxide; ammonium carbonate, lithium carbonate Alkali metal carbonates such as sodium carbonate and potassium carbonate; quaternary ammonium hydroxides such as tetramethylammonium hydroxide and choline; organic amines such as ethylamine, diethylamine, triethylamine and hydroxyethylamine; and ammonia. Is used in one or a mixture of two or more. Of these, alkali metal hydroxides are preferred because they are inexpensive and easy to handle.
本発明の金属ＣＭＰ用研磨組成物は、酸化剤成分を含有してもよい。含有される酸化剤としては、過酸化水素、硝酸、過ヨウ素酸、過ヨウ素酸カリウム、過ヨウ素酸リチウム、過ヨウ素酸ナトリウム、過マンガン酸カリウム、過マンガン酸リチウム、過マンガン酸ナトリウム、重クロム酸、重クロム酸カリウム、重クロム酸リチウム、重クロム酸ナトリウム、過塩素酸、過塩素酸塩（アルカリ金属塩、アンモニウム塩など）、次亜塩素酸、次亜塩素酸塩（アルカリ金属塩、アンモニウム塩など）、過硫酸、過硫酸塩（アルカリ金属塩、アンモニウム塩など）、過酢酸、ｔ−ブチルハイドロパーオキサイド、過安息香酸およびオゾンなどが挙げられ、これらは１種類または２種類以上の混合物で使用される。 The polishing composition for metal CMP of the present invention may contain an oxidant component. The oxidizers included are hydrogen peroxide, nitric acid, periodic acid, potassium periodate, lithium periodate, sodium periodate, potassium permanganate, lithium permanganate, sodium permanganate, and heavy chromium. Acids, potassium dichromate, lithium dichromate, sodium dichromate, perchloric acid, perchlorates (alkali metal salts, ammonium salts, etc.), hypochlorous acid, hypochlorites (alkali metal salts, Ammonium salts), persulfuric acid, persulfates (alkali metal salts, ammonium salts, etc.), peracetic acid, t-butyl hydroperoxide, perbenzoic acid and ozone. Used in a mixture.
本発明の金属ＣＭＰ用研磨組成物中の酸化剤成分の好ましい含有量は０．０１〜１０質量％である。含有量が上記下限より少ないと充分な研磨速度が得られない場合があり、一方、含有量が上記上限より多いとエッチングを制御できなくなり、ディッシングなどの不具合の原因となる場合がある。 The preferable content of the oxidizing agent component in the metal CMP polishing composition of the present invention is 0.01 to 10% by mass. If the content is less than the lower limit, a sufficient polishing rate may not be obtained. On the other hand, if the content is higher than the upper limit, etching cannot be controlled, which may cause problems such as dishing.
本発明の金属ＣＭＰ用研磨組成物に含有される酸化剤として好適なのは、過硫酸アンモニウムである。過硫酸アンモニウムは、他の酸化剤に対して、研磨速度とエッチング抑制のコントロールが容易である利点を有する。過硫酸アンモニウムを酸化剤成分として用いた場合の含有量は、０．０１〜５質量％が好ましく、０．１〜２．５質量％がより好ましい。 A suitable oxidizing agent contained in the metal CMP polishing composition of the present invention is ammonium persulfate. Ammonium persulfate has an advantage that the polishing rate and the etching suppression can be easily controlled with respect to other oxidizing agents. The content when ammonium persulfate is used as the oxidizing agent component is preferably 0.01 to 5 mass%, more preferably 0.1 to 2.5 mass%.
本発明の金属ＣＭＰ用研磨組成物は、研磨抑制、各成分の溶解または分散安定性、消泡性などを付与するために界面活性剤を含有してもよい。含有される界面活性剤としては、ノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、ベタイン系界面活性剤が挙げられ、これらは１種類または２種類以上の混合物で使用される。 The polishing composition for metal CMP of the present invention may contain a surfactant in order to impart polishing suppression, dissolution or dispersion stability of each component, antifoaming property, and the like. Examples of the surfactant to be contained include nonionic surfactants, anionic surfactants, cationic surfactants, and betaine surfactants, which are used in one kind or a mixture of two or more kinds. .
本発明の金属ＣＭＰ用研磨組成物中の界面活性剤成分の好ましい含有量は０．０００１〜１０質量％である。含有量が上記下限より少ないと充分な使用効果が得られない場合があり、一方、含有量が上記上限より多いと研磨速度が低下する場合がある。 The preferable content of the surfactant component in the metal CMP polishing composition of the present invention is 0.0001 to 10% by mass. If the content is less than the above lower limit, a sufficient use effect may not be obtained. On the other hand, if the content is more than the above upper limit, the polishing rate may be reduced.
本発明の金属ＣＭＰ用研磨組成物に含有される界面活性剤として好適なのは、アニオン系界面活性剤である。アニオン系界面活性剤としては、例えば、高級脂肪酸塩、高級アルコール硫酸エステル塩、硫化オレフィン塩、高級アルキルスルホン酸塩、α−オレフィンスルホン酸塩、硫酸化脂肪酸塩、スルホン化脂肪酸塩、リン酸エステル塩、脂肪酸エステルの硫酸エステル塩、グリセライド硫酸エステル塩、脂肪酸エステルのスルホン酸塩、α−スルホ脂肪酸メチルエステル塩、ポリオキシアルキレンアルキルエーテル硫酸エステル塩、ポリオキシアルキレンアルキルフェニルエーテル硫酸エステル塩、ポリオキシアルキレンアルキルエーテルカルボン酸塩、アシル化ペプチド、脂肪酸アルカノールアミドまたはそのアルキレンオキサイド付加物の硫酸エステル塩、スルホコハク酸エステル、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルキルベンゾイミダゾールスルホン酸塩、ポリオキシアルキレンスルホコハク酸塩、Ｎ−アシル−Ｎ−メチルタウリンの塩、Ｎ−アシルグルタミン酸またはその塩、アシルオキシエタンスルホン酸塩、アルコキシエタンスルホン酸塩、Ｎ−アシル−β−アラニンまたはその塩、Ｎ−アシル−Ｎ−カルボキシエチルタウリンまたはその塩、Ｎ−アシル−Ｎ−カルボキシメチルグリシンまたはその塩、アシル乳酸塩、Ｎ−アシルサルコシン塩、およびアルキルまたはアルケニルアミノカルボキシメチル硫酸塩などの１種または２種以上の混合物を挙げることができる。 An anionic surfactant is suitable as the surfactant contained in the metal CMP polishing composition of the present invention. Examples of the anionic surfactant include higher fatty acid salts, higher alcohol sulfate esters, sulfurized olefin salts, higher alkyl sulfonates, α-olefin sulfonates, sulfated fatty acid salts, sulfonated fatty acid salts, and phosphate esters. Salt, sulfate ester of fatty acid ester, glyceride sulfate ester salt, sulfonate salt of fatty acid ester, α-sulfo fatty acid methyl ester salt, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl phenyl ether sulfate ester salt, polyoxy Alkylene alkyl ether carboxylates, acylated peptides, sulfate esters of fatty acid alkanolamides or alkylene oxide adducts thereof, sulfosuccinates, alkylbenzene sulfonates, alkylnaphthalene sulfones Sulfonate, alkyl benzimidazole sulfonate, polyoxyalkylene sulfosuccinate, N-acyl-N-methyltaurine salt, N-acyl glutamic acid or salt thereof, acyloxyethane sulfonate, alkoxy ethane sulfonate, N -Acyl-β-alanine or salts thereof, N-acyl-N-carboxyethyltaurine or salts thereof, N-acyl-N-carboxymethylglycine or salts thereof, acyl lactates, N-acyl sarcosine salts, and alkyl or alkenyl Mention may be made of one kind or a mixture of two or more kinds such as aminocarboxymethyl sulfate.
本発明の金属ＣＭＰ用研磨組成物は、研磨された金属を溶出させる金属溶出剤成分を含有してもよい。銅ＣＭＰの場合、含有される金属（銅）溶出剤としては、上記の有機酸成分で例示した有機酸のアンモニウム塩およびアルカリ金属塩が挙げられ、これらは１種類または２種類以上の混合物で使用される。 The metal CMP polishing composition of the present invention may contain a metal eluent component that elutes the polished metal. In the case of copper CMP, the contained metal (copper) eluent includes ammonium salts and alkali metal salts of organic acids exemplified in the above organic acid component, and these are used in one kind or a mixture of two or more kinds. Is done.
上記の銅溶出剤の好ましい含有量は０．０１〜１０質量％である。含有量が上記下限より少ないと充分な研磨速度が得られない場合があり、一方、含有量が上記上限より多いと過剰なエッチングを制御できなくなる場合がある。 The preferable content of the copper eluent is 0.01 to 10% by mass. If the content is less than the above lower limit, a sufficient polishing rate may not be obtained. On the other hand, if the content is more than the above upper limit, excessive etching may not be controlled.
また、上記の銅溶出剤として好適なのは、脂肪族有機カルボン酸のアンモニウム塩であり、特にシュウ酸、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、フマル酸、シュウ酸、リンゴ酸、酒石酸およびクエン酸のアンモニウム塩が好ましく、さらには、バリア層との選択研磨性に優れるので、シュウ酸二アンモニウムが好ましい。シュウ酸二アンモニウムの配合量は０．０５〜２質量％であり、０．１〜１質量％がより好ましい。 Also suitable as the copper eluent is an ammonium salt of an aliphatic organic carboxylic acid, particularly oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, oxalic acid, Ammonium salts of malic acid, tartaric acid and citric acid are preferred, and diammonium oxalate is preferred because of excellent selective polishing with the barrier layer. The blending amount of diammonium oxalate is 0.05 to 2% by mass, and more preferably 0.1 to 1% by mass.
本発明の金属ＣＭＰ用研磨組成物は、上記説明の有機性成分を安定に溶解させるために可溶化剤成分を含有してもよい。含有される可溶化剤成分としては、メタノール、エタノールなどのアルコール類；アセトン、メチルエチルケトンなどのケトン類；ジエチルエーテル、テトラヒドロフラン、ジオキサンなどのエーテル類；エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテルなどのアルキレングリコールモノアルキルエーテル類；エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、２−メチル−１，３−プロパンジオール、グリセリン、ペンタエリスリトール、ジペンタエリスリトール、テトラメチロールプロパンなどのポリアルコール類；Ｎ−メチルピロリドンなどのピロリドン類が挙げられ、これらは１種類または２種類以上の混合物で使用される。 The polishing composition for metal CMP of the present invention may contain a solubilizer component in order to stably dissolve the organic component described above. Containing solubilizer components include alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, tetrahydrofuran and dioxane; alkylene glycols such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether Monoalkyl ethers; polyalcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, glycerin, pentaerythritol, dipentaerythritol, and tetramethylolpropane Pyrrolidones such as N-methylpyrrolidone, which are used in one kind or a mixture of two or more kinds;
本発明の金属ＣＭＰ用研磨組成物中の可溶化剤成分の好ましい含有量は０．０１〜１０質量％である。含有量が上記下限より少ないと充分な使用効果が得られない場合があり、一方、含有量が上記上限より多いと研磨面の表面荒れが生じる場合がある。 The preferable content of the solubilizer component in the polishing composition for metal CMP of the present invention is 0.01 to 10% by mass. If the content is less than the above lower limit, a sufficient use effect may not be obtained. On the other hand, if the content is more than the upper limit, surface roughness of the polished surface may occur.
本発明の金属ＣＭＰ用研磨組成物に含有される可溶化剤成分としては、必須成分である前記一般式（１）で表される化合物に対する可溶化効果が特に優れるのでＮ−メチルピロリドンが好適である。Ｎ−メチルピロリドンの好ましい含有量は０．０５〜１質量％である。 As the solubilizer component contained in the metal CMP polishing composition of the present invention, N-methylpyrrolidone is suitable because the solubilizing effect on the compound represented by the general formula (1), which is an essential component, is particularly excellent. is there. The preferable content of N-methylpyrrolidone is 0.05 to 1% by mass.
本発明の金属ＣＭＰ用研磨組成物は、他の添加剤成分を含有してもよい。他の添加剤成分としては、ｐＨ緩衝作用、防錆作用を付与するために用いられるグリシン、アラニンなどのアミノ酸化合物、ウエハの有機物汚染を低減させる効果のある有機化合物を包接するα−、β−またはγ−シクロデキストリンなどの包接化合物、研磨面の表面平滑性を付与するイセチオン酸脂肪酸エステルなどのヒドロキシアルカンスルホン酸脂肪酸エステル類など、砥粒表面の清浄化作用を付与することで、砥粒の分散安定性および研磨能力を向上させるモノエタノールアミン、ジエタノールアミン、トリエタノールアミン、２−ジメチルアミノエタノール、２−（２−アミノエチルアミノ）エタノール、Ｎ−メチルジエタノールアミンなどのアルカノールアミン類が挙げられる。これらのその他の添加剤成分を使用する場合は、その使用量は０．０００１〜１０質量％、好ましくは０．０００５〜５質量％となる範囲で配合される。 The metal CMP polishing composition of the present invention may contain other additive components. Examples of other additive components include pH buffering action, amino acid compounds such as glycine and alanine used for imparting rust prevention action, and α-, β- inclusions of organic compounds effective to reduce organic contamination of the wafer. Or by adding a cleaning action on the surface of the abrasive grains, such as inclusion compounds such as γ-cyclodextrin, hydroxyalkane sulfonic acid fatty acid esters such as isethionic acid fatty acid esters that impart surface smoothness of the polished surface, etc. And alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, 2-dimethylaminoethanol, 2- (2-aminoethylamino) ethanol, and N-methyldiethanolamine which improve the dispersion stability and polishing ability. When these other additive components are used, the amount used is 0.0001 to 10% by mass, preferably 0.0005 to 5% by mass.
本発明の金属ＣＭＰ用研磨組成物は、上記した各成分を上記したような含有量で含んでなるが、残りは水である。従って、上記に挙げた各成分を規定した量で含む金属ＣＭＰ用研磨組成物となるように、水を加えて１００質量％とする。 The polishing composition for metal CMP of the present invention comprises the above-described components in the amounts as described above, with the remainder being water. Accordingly, water is added to a content of 100% by mass so as to obtain a polishing composition for metal CMP containing the above-mentioned components in prescribed amounts.
本発明の金属ＣＭＰ用研磨組成物の調製は、上記で説明した各成分と水を混合し、均一に分散溶解すればよい。この場合に全ての成分を混合して１液タイプの組成物としてもよく、２液タイプの組成物としてもよい。２液タイプの組成物としては、例えば、酸化剤成分のみ別成分とし、他の全ての成分の混合物との２液タイプが挙げられる。 The metal CMP polishing composition of the present invention may be prepared by mixing each component described above and water and uniformly dispersing and dissolving them. In this case, all components may be mixed to form a one-component type composition or a two-component type composition. Examples of the two-component type composition include a two-component type in which only the oxidizing agent component is a separate component and a mixture of all other components.
次に実施例および比較例を挙げて本発明をさらに詳細に説明する。しかしながら、本発明は以下の実施例などによって何ら制限を受けるものではない。 Next, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited by the following examples.
［実施例１〜４、比較例１〜３］
前記例示化合物Ｎｏ．２、ベンゾトリアゾール、粒径が１００ｎｍのコロイダルシリカ、過硫酸アンモニウム、シュウ酸二アンモニウム１水和物、ドデシルベンゼンスルホン酸、ナフタレン−２−スルホン酸、ポリビニルピロリドン（Luvitec K30 Pulver BASF社製；数平均分子量１０，０００）、Ｎ−メチルピロリドンおよびグリシンを表１に示す割合（質量％）で、全体が１００質量％になる量の水に混合し、各種金属ＣＭＰ用研磨組成物を調製した。なお、ｐＨ調整剤は水酸化カリウムを使用し、すべての組成物のｐＨを９．０に調整した。
[Examples 1-4, Comparative Examples 1-3]
In the exemplified compound No. 2, benzotriazole, colloidal silica having a particle size of 100 nm, ammonium persulfate, diammonium oxalate monohydrate, dodecylbenzenesulfonic acid, naphthalene-2-sulfonic acid, polyvinylpyrrolidone (manufactured by Luvitec K30 Pulver BASF; number average molecular weight) 10,000), N-methylpyrrolidone and glycine were mixed in water (100% by mass) in the proportions (mass%) shown in Table 1 to prepare various metal CMP polishing compositions. In addition, the pH adjuster used potassium hydroxide and adjusted the pH of all the compositions to 9.0.
［評価例１］
被研磨体として、電解めっき法で銅膜を１，０００ｎｍ成膜したウエハを３×３ｃｍ正方形に切断し、上記実施例１〜４および比較例１〜３で得た各金属ＣＭＰ用研磨組成物を用いて、それぞれの成膜面を下記の条件で研磨した。研磨終了後、ウエハを洗浄乾燥し、銅膜の各研磨速度を求めた。得られた結果を表２に示す。なお、研磨速度は、研磨前後の膜厚の差をLoresta GP（三菱化学製）を使用して測定して求めた。
（条件）
研磨機：ＮＦ−３００（ナノファクター製）
研磨パッド：ＩＣ１４００（ＸＹ溝付）（ロデールニッタ製）
研磨時間：３分間（銅膜）
定盤回転数：６０ｒｐｍ
キャリア回転数：６０ｒｐｍ
研磨加工圧力：１ｐｓｉ
研磨液供給速度：５０ｍｌ／分
[Evaluation Example 1]
A polishing composition for metal CMP obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was obtained by cutting a wafer having a copper film of 1,000 nm formed by electrolytic plating as a body to be polished, and cutting it into 3 × 3 cm squares. Each film-forming surface was polished using the following conditions. After polishing, the wafer was washed and dried, and each polishing rate of the copper film was determined. The obtained results are shown in Table 2. The polishing rate was determined by measuring the difference in film thickness before and after polishing using Loresta GP (manufactured by Mitsubishi Chemical).
(conditions)
Polishing machine: NF-300 (manufactured by Nano Factor)
Polishing pad: IC1400 (with XY groove) (Rodel Nitta)
Polishing time: 3 minutes (copper film)
Plate rotation speed: 60rpm
Carrier rotation speed: 60rpm
Polishing pressure: 1 psi
Polishing liquid supply rate: 50 ml / min
上記表２より、本発明の金属ＣＭＰ用研磨組成物である実施例１〜４と防食剤を使用しない比較例１とを比べると銅の研磨速度の低下が小さいことが確認できる。これに対して、防食剤にベンゾトリアゾールを用いた比較例２、３と比較例１とを比べると銅の研磨速度が大きく損なわれていることが確認できる。 From Table 2 above, it can be confirmed that the decrease in the polishing rate of copper is small when Examples 1-4 which are polishing compositions for metal CMP of the present invention are compared with Comparative Example 1 which does not use an anticorrosive agent. On the other hand, when Comparative Examples 2 and 3 using benzotriazole as an anticorrosive agent are compared with Comparative Example 1, it can be confirmed that the polishing rate of copper is greatly impaired.
［実施例５〜１０］
前記例示化合物Ｎｏ．２が０．００１質量％、粒径１００ｎｍのコロイダルシリカが０．１質量％、過硫酸アンモニウムが１質量％、シュウ酸二アンモニウム１水和物が０．４質量％、ドデシルベンゼンスルホン酸が０．０３質量％、表３に記載のポリアルキレングリコールが０．０３質量％およびグリシンが０．０２質量％の濃度となるように水と混合し、各種金属ＣＭＰ用研磨組成物を調製した。なお、ｐＨ調整剤は水酸化カリウムを使用し、すべての組成物のｐＨを９．０に調整した。
[Examples 5 to 10]
In the exemplified compound No. 2 is 0.001% by mass, colloidal silica having a particle size of 100 nm is 0.1% by mass, ammonium persulfate is 1% by mass, diammonium oxalate monohydrate is 0.4% by mass, and dodecylbenzenesulfonic acid is 0.8%. Various metal CMP polishing compositions were prepared by mixing with water so that the concentration of 03% by mass, polyalkylene glycol described in Table 3 was 0.03% by mass, and glycine was 0.02% by mass. In addition, the pH adjuster used potassium hydroxide and adjusted the pH of all the compositions to 9.0.
［評価例２］
金属ＣＭＰ用研磨組成物を上記実施例５〜９で得たものに変えた以外は、前記評価例１と同様の評価を行った。結果を表４に示す。
[Evaluation Example 2]
Evaluation similar to the said evaluation example 1 was performed except having changed the polishing composition for metal CMP into what was obtained in the said Examples 5-9. The results are shown in Table 4.
［評価例３］
プラズマＣＶＤ法で酸化ケイ素膜を３００ｎｍ成膜したウエハを作成し、これを３×３ｃｍの形状に切断した。これについて酸化ケイ素中に深さ２５０ｎｍの溝を作成し、スパッタリング法で窒化タンタル膜を１５ｎｍ、その上面にタンタル膜を１５ｎｍ、さらに電解めっき法により銅膜８００ｎｍを形成したものを平坦性評価用試験片とした。この評価試験片において研磨時間を４分とし、表５に記載の金属ＣＭＰ用研磨組成物を用いた他は、前記評価例１と同様の条件で研磨を行った。この研磨した試験片について、平坦性と表面状態をＡＦＭ（原子間力顕微鏡）（セイコーインスツルメンツ製 Nanopics）を用いて評価した。平坦性についてはウエハ表面の最凸部と最凹部の段差を測定し、表面荒れについては目視で判断し、荒れが観察されなかったものを○、荒れが観察されたものを×とした。結果を表５に示す。
[Evaluation Example 3]
A wafer on which a silicon oxide film having a thickness of 300 nm was formed by plasma CVD was cut into a 3 × 3 cm shape. About this, a groove having a depth of 250 nm is formed in silicon oxide, a tantalum nitride film of 15 nm by sputtering, a tantalum film of 15 nm on the upper surface, and a copper film of 800 nm formed by electrolytic plating are tested for flatness evaluation. It was a piece. The evaluation test piece was polished under the same conditions as in Evaluation Example 1 except that the polishing time was 4 minutes and the metal CMP polishing composition shown in Table 5 was used. The polished specimen was evaluated for flatness and surface condition using an AFM (Atomic Force Microscope) (Nanopics manufactured by Seiko Instruments Inc.). Regarding the flatness, the level difference between the most convex part and the most concave part on the wafer surface was measured, and the surface roughness was judged by visual observation. The case where the roughness was not observed was evaluated as “◯”, and the case where the roughness was observed as “X”. The results are shown in Table 5.
上記表５より、本発明の金属ＣＭＰ用研磨組成物である実施例１〜４は、平坦性および表面荒れに対して効果を示すことが確認できた。また、実施例１と実施例２から、有機酸成分としてドデシルベンゼンスルホン酸とナフタレン−２−スルホン酸を用いると特に優れた平坦性を示すことが確認できた。 From the said Table 5, it has confirmed that Examples 1-4 which are polishing compositions for metal CMP of this invention showed an effect with respect to flatness and surface roughness. Further, from Examples 1 and 2, it was confirmed that particularly excellent flatness was exhibited when dodecylbenzenesulfonic acid and naphthalene-2-sulfonic acid were used as the organic acid component.
以上の如き本発明によれば、半導体装置の製造に当たって、特にダマシン法により銅配線を形成する際に、研磨後の平坦性および表面状態が良好であり、銅層に対する充分な研磨速度を有する銅層の除去に好ましく使用できる金属ＣＭＰ用研磨組成物を提供することができる。
According to the present invention as described above, in the manufacture of a semiconductor device, particularly when forming a copper wiring by a damascene method, the flatness and surface state after polishing are good, and the copper layer has a sufficient polishing rate for the copper layer. A polishing composition for metal CMP which can be preferably used for removing a layer can be provided.
Claims (9)
The polishing composition for metal CMP according to any one of claims 3 to 7, wherein the water-soluble polymer component is a polyalkylene glycol.
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| WO2009128494A1 (en) * | 2008-04-16 | 2009-10-22 | 日立化成工業株式会社 | Polishing solution for cmp and polishing method |
| JP2011032135A (en) * | 2009-08-03 | 2011-02-17 | Adeka Corp | Stabilizer used for peroxy-monosulfuric acid aqueous solution |
| JP2011505694A (en) * | 2007-11-27 | 2011-02-24 | キャボット マイクロエレクトロニクス コーポレイション | CMP composition and method for passivating copper |
| WO2012161202A1 (en) * | 2011-05-24 | 2012-11-29 | 株式会社クラレ | Erosion inhibitor for chemical mechanical polishing, slurry for chemical mechanical polishing, and chemical mechanical polishing method |
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| JP2011505694A (en) * | 2007-11-27 | 2011-02-24 | キャボット マイクロエレクトロニクス コーポレイション | CMP composition and method for passivating copper |
| WO2009128494A1 (en) * | 2008-04-16 | 2009-10-22 | 日立化成工業株式会社 | Polishing solution for cmp and polishing method |
| JP2014057071A (en) * | 2008-04-16 | 2014-03-27 | Hitachi Chemical Co Ltd | Polishing liquid for cmp and polishing method |
| JP5513372B2 (en) * | 2008-04-16 | 2014-06-04 | 日立化成株式会社 | Polishing liquid and polishing method for CMP |
| JP2011032135A (en) * | 2009-08-03 | 2011-02-17 | Adeka Corp | Stabilizer used for peroxy-monosulfuric acid aqueous solution |
| JPWO2011058952A1 (en) * | 2009-11-11 | 2013-04-04 | 株式会社クラレ | Chemical mechanical polishing slurry and substrate polishing method using the same |
| US9536752B2 (en) | 2009-11-11 | 2017-01-03 | Kuraray Co., Ltd. | Slurry for chemical mechanical polishing and polishing method for substrate using same |
| WO2012161202A1 (en) * | 2011-05-24 | 2012-11-29 | 株式会社クラレ | Erosion inhibitor for chemical mechanical polishing, slurry for chemical mechanical polishing, and chemical mechanical polishing method |
| JP7019224B1 (en) | 2021-02-25 | 2022-02-15 | 大同化学株式会社 | Water-soluble rust inhibitor composition and its usage |
| JP2022130273A (en) * | 2021-02-25 | 2022-09-06 | 大同化学株式会社 | Water-soluble rust inhibitor composition and method for using the same |
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