JP2007013059A - Polishing composition for cmp - Google Patents
Polishing composition for cmp Download PDFInfo
- Publication number
- JP2007013059A JP2007013059A JP2005195257A JP2005195257A JP2007013059A JP 2007013059 A JP2007013059 A JP 2007013059A JP 2005195257 A JP2005195257 A JP 2005195257A JP 2005195257 A JP2005195257 A JP 2005195257A JP 2007013059 A JP2007013059 A JP 2007013059A
- Authority
- JP
- Japan
- Prior art keywords
- polishing
- mass
- cmp
- polishing composition
- acid
- 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
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 98
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 39
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 13
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims abstract description 11
- 150000007514 bases Chemical class 0.000 claims abstract description 5
- 239000012964 benzotriazole Substances 0.000 claims description 12
- 239000006061 abrasive grain Substances 0.000 claims description 11
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 claims 1
- 150000003460 sulfonic acids Chemical class 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052802 copper Inorganic materials 0.000 abstract description 25
- 230000004888 barrier function Effects 0.000 abstract description 8
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 235000012431 wafers Nutrition 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000012190 activator Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 229920003169 water-soluble polymer Polymers 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 150000007524 organic acids Chemical class 0.000 description 7
- 229910052715 tantalum Inorganic materials 0.000 description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- -1 anticorrosives Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 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 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 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
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- PLUHAVSIMCXBEX-UHFFFAOYSA-N azane;dodecyl benzenesulfonate Chemical compound N.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 PLUHAVSIMCXBEX-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 1
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- IRDCEJVOXCGYAV-UHFFFAOYSA-M lithium;2-dodecylbenzenesulfonate Chemical compound [Li+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O IRDCEJVOXCGYAV-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
本発明は、ＣＭＰ（Chemical Mechanical Polishing、化学機械研磨）用研磨組成物に関し、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、銅層の除去に好ましく使用されるＣＭＰ用研磨組成物に関する。 TECHNICAL FIELD The present invention relates to a polishing composition for CMP (Chemical Mechanical Polishing), and more particularly to a polishing composition for CMP that is preferably used for removing a copper layer when wiring is formed by a damascene method in manufacturing a semiconductor device. About.
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層のみを、配線部銅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 a surplus copper layer and a barrier metal layer. In the two-stage polishing method often performed in this CMP polishing, only the outermost copper layer is selectively polished in the first stage polishing while suppressing the dishing of the wiring portion copper layer to be smaller than the thickness of the tantalum-based barrier layer, In the second stage polishing, it is desired to selectively polish only the tantalum-based barrier layer exposed after polishing the outermost layer copper layer while suppressing erosion of the insulating film and the wiring portion copper layer. 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ェーハーを載せ、ウェーハー表面にパッドを接触させ、ウェーハー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ェーハー表面が研磨されると同時に、スラリ内の化合物とウェーハー表面の化学反応によりウェーハー表面が平坦化される。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、酸化金属溶解剤、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。 In CMP technology, a wafer to be flattened 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. As components of a polishing composition that can be used in CMP, polishing abrasive grains, metal oxidizers, metal oxide solubilizers, anticorrosives, activators, water-soluble polymer compounds, and the like have been proposed.
特許文献１には、複素環を有する化合物、界面活性剤および酸化剤を含有するＣＭＰ用研磨組成物が開示されている。特許文献１には、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、研磨砥粒としてシリカ、アルミナ、チタニア、ジルコニア、セリアなどが例示されており、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、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、複素環を有する化合物としてベンゾトリアゾールが例示されており、ｐＨ調整剤として、水酸化カリウム、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。 Patent Document 1 discloses a polishing composition for CMP containing a compound having a heterocyclic ring, a surfactant and an oxidizing agent. Patent Document 1 exemplifies dodecylbenzenesulfonic acid or a salt thereof as a surfactant, silica, alumina, titania, zirconia, ceria, etc. as polishing abrasives, and hydrogen peroxide as a metal oxidant. , Ammonium persulfate, cerium ammonium nitrate, potassium periodate, periodate and ozone water are exemplified, formic acid, acetic acid and oxalic acid are exemplified as organic acids, and benzotriazole is exemplified as a compound having a heterocyclic ring Examples of the pH adjuster include inorganic alkali compounds such as potassium hydroxide and sodium hydroxide, and ammonia.
特許文献２には、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を含有するＣＭＰ用研磨組成物が開示されている。特許文献２には、研磨砥粒としてシリカ、アルミナおよびジルコニアなどが例示されており、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、酸化金属溶解剤としてギ酸、酢酸、シュウ酸、リンゴ酸およびクエン酸などが例示されており、防食剤としてトリアゾールおよびベンゾトリアゾールなどのトリアゾール類が例示されており、水溶性ポリマーとして寒天などの多糖類およびポリアスパラギン酸などのポリカルボン酸、これらのポリカルボン酸塩およびポリビニルピロリドンなどのビニル系ポリマーが例示されている。 Patent Document 2 discloses a polishing composition for CMP containing an oxidant, a metal oxide solubilizer, a metal anticorrosive, and a compound capable of lowering the potential of copper or a copper alloy. Patent Document 2 exemplifies silica, alumina, zirconia and the like as abrasive grains, and hydrogen peroxide, nitric acid, potassium periodate, hypochlorite, persulfate and ozone water are used as metal oxidizers. Examples of the metal oxide solubilizer include formic acid, acetic acid, oxalic acid, malic acid and citric acid, and examples of the anticorrosive agent include triazoles such as triazole and benzotriazole, and examples of the water-soluble polymer include Examples include polysaccharides such as agar and polycarboxylic acids such as polyaspartic acid, these polycarboxylic acid salts and vinyl polymers such as polyvinylpyrrolidone.
ＣＭＰ用研磨組成物は、上記のような様々な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るが、表面状態や研磨速度や研磨選択性などの要求性能については、いまだ改善の余地がある。上記特許文献１に記載の技術ではディッシングやエロージョンの問題があり、特許文献２に記載の技術では銅の選択研磨性に問題がある。
本発明においては、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し、かつバリア層との研磨速度の差が大きいＣＭＰ用研磨組成物を提供することを課題とする。 In the present invention, it is a polishing composition for CMP that gives good flatness and good surface condition on a metal surface after polishing by CMP, has a sufficient copper polishing rate, and polishes with a barrier layer. It is an object of the present invention to provide a polishing composition for CMP having a large difference.
本発明者らは、上記課題を解決するため鋭意研究の結果、特定の組成からなる組成物が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、研磨砥粒０．１〜１０質量％、過硫酸アンモニウム０．０１〜１０質量％、シュウ酸０．０１〜５質量％、ベンゾトリアゾール０．０００１〜５質量％、ドデシルベンゼンスルホン酸および／またはドデシルベンゼンスルホン酸の塩０．００１〜１０質量％、ポリビニルピロリドン０．００１〜１０質量％および水溶性塩基性化合物であるｐＨ調整剤を含有し、ｐＨが８〜１２の範囲にあることを特徴とするＣＭＰ用研磨組成物を提供する。
As a result of intensive studies to solve the above problems, the present inventors have found that a composition having a specific composition is effective, and have reached the present invention.
That is, the present invention comprises abrasive grains 0.1 to 10% by mass, ammonium persulfate 0.01 to 10% by mass, oxalic acid 0.01 to 5% by mass, benzotriazole 0.0001 to 5% by mass, dodecylbenzenesulfone. Acid and / or salt of dodecylbenzenesulfonic acid 0.001 to 10% by mass, polyvinyl pyrrolidone 0.001 to 10% by mass and a pH adjuster which is a water-soluble basic compound, and the pH is in the range of 8 to 12. There is provided a polishing composition for CMP.
上記本発明においては、ポリビニルピロリドンの数平均分子量が５，０００〜１００，０００であることが好ましい。 In the said invention, it is preferable that the number average molecular weights of polyvinylpyrrolidone are 5,000-100,000.
本発明によれば、半導体装置の製造に当って、特にダマシン法により配線を形成する際に、表面平滑性に優れ、銅層に対する高い研磨選択性を有し、銅層の除去に好ましく使用できるＣＭＰ用研磨組成物が提供される。 According to the present invention, in manufacturing a semiconductor device, particularly when a wiring is formed by a damascene method, it has excellent surface smoothness, high polishing selectivity for a copper layer, and can be preferably used for removing a copper layer. A polishing composition for CMP is provided.
次に好ましい実施形態を挙げて本発明をさらに詳しく説明する。
本発明のＣＭＰ用研磨組成物に含有される研磨砥粒としては、基本的にＣＭＰ研磨材として用いられる、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などを全て用いることができるが、一般には安定性などの面から、二酸化ケイ素を用いることが望ましく、その中でもコロイダルシリカが最も好ましい。
Next, the present invention will be described in more detail with reference to preferred embodiments.
As polishing abrasive grains contained in the polishing composition for CMP of the present invention, silicon dioxide, aluminum oxide, cerium oxide, silicon nitride, zirconium oxide, silicon carbide, manganese dioxide, etc., which are basically used as CMP abrasives. Although all can be used, it is generally desirable to use silicon dioxide from the viewpoint of stability and the like, and among these, colloidal silica is most 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ＣＭＰ用研磨組成物においてはその粒径が１〜３００ｎｍの範囲が好ましく、５〜１００ｎｍの範囲がさらに好ましい。本発明の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うえから０．１〜１０質量％である。研磨砥粒の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、研磨砥粒の含有量が上記上限より多いとエロージョン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０．２〜５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 polishing composition for CMP of the present invention, the particle diameter is preferably in the range of 1 to 300 nm, and more preferably in the range of 5 to 100 nm. In order to improve the flatness of the polished surface, the content of the abrasive grains in the CMP polishing composition of the present invention is 0.1 to 10% by mass. When the content of the abrasive grains is less than the above lower limit, the polishing rate becomes slow. On the other hand, when the content of the abrasive grains is more than the above upper limit, it is difficult to suppress erosion. The content of the abrasive grains is more preferably in the range of 0.2 to 5% by mass.
本発明のＣＭＰ用研磨組成物に含有される酸化剤は、過硫酸アンモニウムである。過硫酸アンモニウムは、他の酸化剤と比較して銅に対する酸化力が強いという利点を有する。例えば、同量の過酸化水素を用いた場合と比較すると３倍以上である。本発明のＣＭＰ研磨用組成物における過硫酸アンモニウムの含有量は、研磨速度や研磨面の平坦性を向上させるうえから０．０１〜１０質量％である。過硫酸アンモニウムの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、過硫酸アンモニウムの含有量が上記上限より多いとエッチングやディッシングの抑制が困難になり、また、取扱いの点でも危険となる。従って過硫酸アンモニウムの含有量は、０．０１〜１０質量％であり、０．０５〜５質量％の範囲が好ましい。 The oxidizing agent contained in the CMP polishing composition of the present invention is ammonium persulfate. Ammonium persulfate has the advantage that it has a strong oxidizing power for copper compared to other oxidizing agents. For example, it is 3 times or more compared with the case where the same amount of hydrogen peroxide is used. The content of ammonium persulfate in the CMP polishing composition of the present invention is 0.01 to 10% by mass for improving the polishing rate and the flatness of the polished surface. If the ammonium persulfate content is less than the above lower limit, the polishing rate becomes slow. On the other hand, if the ammonium persulfate content is higher than the upper limit, it becomes difficult to suppress etching and dishing, and it is also dangerous in terms of handling. Therefore, the content of ammonium persulfate is 0.01 to 10% by mass, preferably 0.05 to 5% by mass.
本発明のＣＭＰ用研磨組成物に含有される有機酸は、シュウ酸である。シュウ酸は、他の有機酸と比較して、銅層の研磨レートが大きいという利点を有する。本発明のＣＭＰ用研磨組成物におけるシュウ酸の含有量は、研磨面の平坦性を向上させるうえから０．０１〜５質量％である。シュウ酸の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、シュウ酸の含有量が上記上限より多いとディッシングやエロージョンの抑制が難しくなるという難点がある。シュウ酸の含有量は０．０５〜３質量％の範囲が好ましい。 The organic acid contained in the polishing composition for CMP of the present invention is oxalic acid. Oxalic acid has the advantage that the polishing rate of the copper layer is large compared to other organic acids. The content of oxalic acid in the polishing composition for CMP of the present invention is 0.01 to 5% by mass for improving the flatness of the polished surface. When the content of oxalic acid is less than the above lower limit, the polishing rate is slowed. On the other hand, when the content of oxalic acid is larger than the above upper limit, it is difficult to suppress dishing and erosion. The content of oxalic acid is preferably in the range of 0.05 to 3% by mass.
本発明のＣＭＰ用研磨組成物に含有される防食剤は、ベンゾトリアゾールである。ベンゾトリアゾールは、他の防食剤と比較して防食効果が大きいという利点を有する。本発明のＣＭＰ用研磨組成物におけるベンゾトリアゾールの含有量は、研磨面の平坦性を向上させるうえから０．０００１〜５質量％である。ベンゾトリアゾールの含有量が上記下限より少ないとディッシングやエロージョンの抑制が難しくなり、一方、ベンゾトリアゾールの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。ベンゾトリアゾールの含有量は０．０００５〜１質量％の範囲が好ましい。 The anticorrosive contained in the polishing composition for CMP of the present invention is benzotriazole. Benzotriazole has the advantage that it has a greater anticorrosive effect than other anticorrosive agents. The content of benzotriazole in the polishing composition for CMP of the present invention is 0.0001 to 5% by mass for improving the flatness of the polished surface. When the content of benzotriazole is less than the above lower limit, it is difficult to suppress dishing and erosion. On the other hand, when the content of benzotriazole is more than the above upper limit, there is a problem that the polishing rate becomes slow. The content of benzotriazole is preferably in the range of 0.0005 to 1% by mass.
本発明のＣＭＰ用研磨組成物に含有される活性剤は、ドデシルベンゼンスルホン酸および／またはドデシルベンゼンスルホン酸の塩である。ドデシルベンゼンスルホン酸の塩としては、例えば、ドデシルベンゼンスルホン酸リチウム、ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸カリウムおよびドデシルベンゼンスルホン酸アンモニウムが挙げられる。該活性剤は他の活性剤と比較して研磨面の平坦性に優れ、ＣＰＭ用研磨組成物に優れた保存安定性を与える利点を有する。例えば、ポリエチレングリコールモノノニルフェニルエーテルと比較すると研磨面が大きく改善される。本発明のＣＭＰ用研磨組成物における該活性剤の含有量は、研磨面の平坦性を向上させるうえから０．００１〜１０質量％である。上記活性剤の含有量が上記下限より少ないとディッシングの抑制が困難となり、一方、上記活性剤の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。ドデシルベンゼンスルホン酸および／またはドデシルベンゼンスルホン酸の塩の含有量は０．０００５〜５質量％の範囲が好ましい。 The activator contained in the polishing composition for CMP of the present invention is dodecylbenzenesulfonic acid and / or a salt of dodecylbenzenesulfonic acid. Examples of the salt of dodecylbenzenesulfonic acid include lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, and ammonium dodecylbenzenesulfonate. The activator is excellent in flatness of the polished surface as compared with other activators, and has an advantage of giving excellent storage stability to the CPM polishing composition. For example, the polishing surface is greatly improved as compared with polyethylene glycol monononyl phenyl ether. The content of the activator in the polishing composition for CMP of the present invention is 0.001 to 10% by mass for improving the flatness of the polished surface. If the content of the activator is less than the lower limit, it is difficult to suppress dishing. On the other hand, if the content of the activator is greater than the upper limit, the polishing rate becomes slow. The content of dodecylbenzenesulfonic acid and / or salt of dodecylbenzenesulfonic acid is preferably in the range of 0.0005 to 5 mass%.
本発明のＣＭＰ用研磨組成物に含有される水溶性ポリマーは、ポリビニルピロリドンである。ポリビニルピロリドンは、他の水溶性ポリマー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ＣＭＰ用研磨組成物におけるポリビニルピロリドンの含有量は、バリア層の研磨抑制に効果が発現する０．００１〜１０質量％である。ポリビニルピロリドンの含有量が上記下限より少ないと使用効果が得られなくなり、一方、ポリビニルピロリドンの含有量が上記上限より多くても使用効果の増加は得られないばかりか、銅層のエッチングがおこり、研磨後の表面状態が悪化する。ポリビニルピロリドンの含有量は０．０５〜５質量％の範囲が好ましい。また、ポリビニルピロリドンは数平均分子量が５，０００〜１００，０００であることが好ましい。上記数平均分子量が５，０００より小さいと砥粒の分散安定性が不充分となる場合があり、一方、数平均分子量が１００，０００を超えると充分な研磨速度が得られえない場合がある。 The water-soluble polymer contained in the polishing composition for CMP of the present invention is polyvinyl pyrrolidone. Polyvinyl pyrrolidone has an advantage of suppressing the barrier layer polishing as compared with other water-soluble polymers, 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 content of polyvinyl pyrrolidone in the polishing composition for CMP of the present invention is 0.001 to 10% by mass, which is effective for suppressing polishing of the barrier layer. If the content of polyvinyl pyrrolidone is less than the above lower limit, the use effect can not be obtained, on the other hand, even if the content of polyvinyl pyrrolidone is more than the above upper limit, an increase in the use effect can not be obtained, etching of the copper layer occurs, The surface condition after polishing deteriorates. The content of polyvinyl pyrrolidone is preferably in the range of 0.05 to 5% by mass. The polyvinyl pyrrolidone preferably has a number average molecular weight of 5,000 to 100,000. If the number average molecular weight is less than 5,000, the dispersion stability of the abrasive grains may be insufficient. On the other hand, if the number average molecular weight exceeds 100,000, a sufficient polishing rate may not be obtained. .
本発明のＣＭＰ用研磨組成物に含有されるｐＨ調整剤は、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、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、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、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、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、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。本発明のＣＭＰ用研磨組成物における水溶性塩基性化合物の含有量は、ＣＭＰ用研磨組成物のｐＨが８〜１２の範囲になる量である。ｐＨが８未満であると、充分な研磨速度が得られず、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。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。ｐＨは、９〜１１が好ましい。 The pH adjuster contained in the polishing composition for CMP of the present invention is a water-soluble basic compound. Examples of the compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide and barium hydroxide, ammonium carbonate and lithium carbonate. And 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. Of these, alkali metal hydroxides are preferred because they are inexpensive and easy to handle. The content of the water-soluble basic compound in the CMP polishing composition of the present invention is such an amount that the pH of the CMP polishing composition is in the range of 8-12. When the pH is less than 8, a sufficient polishing rate cannot be obtained. When the pH is less than 6, the barrier layer is polished, and the selective polishing property is lowered. Moreover, if pH is larger than 12, dishing will occur and the surface state will deteriorate. The pH is preferably 9-11.
本発明のＣＭＰ用研磨組成物には、上記の必須成分の他に添加剤成分を含有してもよい。添加剤成分としては、ウェーハー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、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 polishing composition for CMP of the present invention may contain an additive component in addition to the above essential components. The additive component includes an inclusion compound such as α-, β- or γ-cyclodextrin that includes an organic compound effective to reduce organic contamination of the wafer, and isethionate fatty acid ester that imparts surface smoothness to the polished surface. And hydroxyalkanesulfonic acid fatty acid esters. When these other additive components are used, they are blended in the range of 0.0001 to 10% by mass, preferably 0.0005 to 5% by mass.
本発明のＣＭＰ用研磨用組成物は、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ＣＭＰ用研磨組成物となるように、水を加えて全体を１００質量％とする。 The polishing composition for CMP of the present invention comprises the above-described components in the above-described contents, but the rest is water. Therefore, water is added to make the whole 100 mass% so as to obtain a polishing composition for CMP containing the above-mentioned components in prescribed amounts.
本発明の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、１種類または２種類以上の成分、例えば、使用時に酸化剤である過硫酸アンモニウムのみを、他の全ての成分の混合物に配合する２液タイプの組成物としてもよい。 The polishing composition for CMP 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-pack type composition, or one or more components, for example, only ammonium persulfate, which is an oxidizing agent when used, may be a mixture of all other components. It is good also as a 2 liquid type composition mix | blended with.
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。
［実施例１〜３、比較例１〜３］
粒子径が２６ｎｍのコロイダルシリカ、過硫酸アンモニウム、シュウ酸、ベンゾトリアゾール、ドデシルベンゼンスルホン酸およびポリビニルピロリドン（Luvitec K30 Pulver BASF社製；数平均分子量１０，０００）を表１に示す割合で水に混合し、各種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た。一方、被研磨体として、電解めっき法で銅膜を７，５００オングストローム成膜したウェーハー、スパッタリング法で窒化タンタル膜を１５０オングストローム、その上面にタンタルを１５０オングストロームをそれぞれ成膜および積層したウェーハーおよびプラズマＣＶＤ法で酸化ケイ素膜を３，０００オングストローム成膜したウェーハーを作成し、それぞれ３×３ｃｍ形状に切断し、上記の各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。
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.
[Examples 1-3, Comparative Examples 1-3]
Colloidal silica having a particle size of 26 nm, ammonium persulfate, oxalic acid, benzotriazole, dodecylbenzenesulfonic acid and polyvinylpyrrolidone (manufactured by Luvitec K30 Pulver BASF; number average molecular weight 10,000) are mixed in water at the ratio shown in Table 1. Various polishing compositions were prepared. In addition, potassium hydroxide was used for the pH adjuster. On the other hand, as the object to be polished, a wafer in which a copper film is formed by electrolytic plating, 7,500 angstroms, a wafer in which a tantalum nitride film is deposited by sputtering, 150 angstroms, and tantalum is deposited on the upper surface by 150 angstroms. Wafers having a silicon oxide film formed by CVD at 3000 angstroms were prepared, cut into 3 × 3 cm shapes, and each film formation surface was polished under the following conditions using the above polishing compositions. .
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：１分間（タンタル膜）、１分間（銅膜）
定盤回転数：６０ｒｐｍ
キャリア回転数：６０ｒｐｍ
研磨加工圧力：２ｐｓｉ
研磨液供給速度：５０ｍｌ／分
Polishing machine: NF-300 (manufactured by Nano Factor)
Polishing pad: IC1400 (with XY groove) (Rodel Nitta)
Polishing time: 1 minute (tantalum film), 1 minute (copper film)
Plate rotation speed: 60rpm
Carrier rotation speed: 60rpm
Polishing pressure: 2 psi
Polishing liquid supply rate: 50 ml / min
研磨終了後、ウェーハーを洗浄乾燥し、以下に示す装置および方法で、銅およびタンタル膜の各研磨速度を求めた。得られた結果を下記表１に示す。
＜測定装置＞：Loresta GP（三菱化学製）
＜測定方法＞：研磨前後の膜厚差から研磨速度を計算した。
また、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１５０オングストローム、その上面にタンタル膜を１５０オングストローム、さらに電解めっき法により銅膜８，０００オングストロームを形成したものを平滑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２分とした他は、上記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、以下の如く平坦性と表面状態を評価した。
平坦性：○ ウェーハー表面凸部と凹部の高さの差が１０ｎｍ未満
× ウェーハー表面凸部と凹部の高さの差が１０ｎｍ以上
表面状態：○ Ｃｕ配線部に表面荒れなし
× Ｃｕ配線部に表面荒れあり
After polishing, the wafer was washed and dried, and the polishing rates of the copper and tantalum films were determined by the following apparatus and method. The obtained results are shown in Table 1 below.
<Measurement device>: Loresta GP (Mitsubishi Chemical)
<Measuring method>: The polishing rate was calculated from the film thickness difference before and after polishing.
In addition, a trench having a depth of 250 nm is formed in silicon oxide, a tantalum nitride film is 150 angstroms by sputtering, a tantalum film is 150 angstroms on the upper surface, and a copper film 8,000 angstroms is formed by electrolytic plating. It was set as the test piece for smoothness evaluation. The evaluation test piece was polished under the same conditions as described above except that the polishing time was 2 minutes.
The polished specimen was evaluated for flatness and surface condition as follows.
Flatness: ○ Difference in height between wafer surface protrusion and recess is less than 10 nm × Difference in height between wafer surface protrusion and recess is 10 nm or more Surface state: ○ No surface roughness on Cu wiring
× Surface roughness on Cu wiring
上記表１より、本発明のＣＭＰ用研磨組成物である実施例１〜実施例３は、銅とタンタルの選択研磨性が良好であり、優れた平坦性および表面状態を示すことが確認できた。ｐＨの小さい比較例１、２は銅の研磨速度が不充分であり、ｐＨの大きい比較例３は平坦性、研磨後の表面状態が不良である。 From Table 1 above, it was confirmed that Examples 1 to 3 which are polishing compositions for CMP of the present invention have good selective polishing properties of copper and tantalum, and show excellent flatness and surface condition. . In Comparative Examples 1 and 2 having a low pH, the copper polishing rate is insufficient, and in Comparative Example 3 having a high pH, the flatness and the surface state after polishing are poor.
［比較例４〜７］
粒子径が２６ｎｍのコロイダルシリカ、酸化剤、有機酸、ベンゾトリアゾール、活性剤、水溶性ポリマーおよび水酸化カリウムを下記表２に示す割合で水に混合し、各種研磨組成物を調製した。
上記実施例１〜３および比較例１〜３と同様の条件および方法にて評価を行った。結果を下記表２に表す。なお、表中の酸化剤、有機酸、活性剤および水溶性ポリマーについて、特に表示のないものは、酸化剤は過硫酸アンモニウム、有機酸はシュウ酸、活性剤はドデシルベンゼンスルホン酸、水溶性ポリマーはポリビニルピロリドン（Luvitec K30 Pulver）である。
[Comparative Examples 4 to 7]
Colloidal silica having a particle size of 26 nm, an oxidizing agent, an organic acid, benzotriazole, an activator, a water-soluble polymer, and potassium hydroxide were mixed in water in the proportions shown in Table 2 to prepare various polishing compositions.
Evaluation was performed under the same conditions and methods as in Examples 1 to 3 and Comparative Examples 1 to 3. The results are shown in Table 2 below. Regarding the oxidizing agents, organic acids, activators, and water-soluble polymers in the table, unless otherwise indicated, the oxidizing agents are ammonium persulfate, the organic acids are oxalic acid, the activators are dodecylbenzenesulfonic acid, and the water-soluble polymers are Polyvinylpyrrolidone (Luvitec K30 Pulver).
上記表２より、本発明のＣＭＰ用研磨組成物の酸化剤を過酸化水素に代えた比較例４は銅層の研磨速度が不充分であった。また、有機酸をリンゴ酸に代えた比較例５は銅層の研磨速度がやや劣り、表面状態が不良であった。また、活性剤をポリエチレングリコールモノノニルフェニルエーテルに代えた比較例６は表面状態が不良であった。また、水溶性ポリマーをポリエチレングリコールに代えた比較例７は、Ｔａ研磨の抑制が不充分で、平坦性が不良であった。これらの結果および上記表１の実施例２から、本発明のＣＭＰ用研磨組成物は、研磨選択性および表面平滑性、表面状態において優れた特性を示す配合であることが確認できた。 From Table 2 above, Comparative Example 4 in which the oxidizing agent of the CMP polishing composition of the present invention was replaced with hydrogen peroxide had an insufficient polishing rate for the copper layer. Moreover, the comparative example 5 which replaced the organic acid with malic acid had a slightly inferior polishing rate of the copper layer, and the surface state was poor. Further, Comparative Example 6 in which the activator was replaced with polyethylene glycol monononyl phenyl ether had a poor surface condition. In Comparative Example 7 in which the water-soluble polymer was replaced with polyethylene glycol, the Ta polishing was not sufficiently suppressed and the flatness was poor. From these results and Example 2 in Table 1 above, it was confirmed that the CMP polishing composition of the present invention was a compound showing excellent polishing selectivity, surface smoothness, and surface properties.
本発明のＣＭＰ用研磨組成物は、半導体装置の製造に当って、特にダマシン法により配線を形成する際に、表面平滑性に優れ、銅層に対する高い研磨選択性を有し、銅層の除去に好ましく使用することができる。
The polishing composition for CMP of the present invention has excellent surface smoothness and high polishing selectivity for a copper layer, particularly when a wiring is formed by a damascene method in the manufacture of a semiconductor device. Can be preferably used.
Claims (2)
The polishing composition for CMP according to claim 1, wherein the polyvinyl pyrrolidone has a number average molecular weight of 5,000 to 100,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005195257A JP2007013059A (en) | 2005-07-04 | 2005-07-04 | Polishing composition for cmp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005195257A JP2007013059A (en) | 2005-07-04 | 2005-07-04 | Polishing composition for cmp |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2007013059A true JP2007013059A (en) | 2007-01-18 |
Family
ID=37751121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005195257A Pending JP2007013059A (en) | 2005-07-04 | 2005-07-04 | Polishing composition for cmp |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2007013059A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011136387A1 (en) * | 2010-04-28 | 2011-11-03 | 株式会社バイコウスキージャパン | Sapphire polishing slurry and sapphire polishing method |
| JP2013043893A (en) * | 2011-08-22 | 2013-03-04 | Jsr Corp | Aqueous dispersion for chemical and mechanical polishing and chemical and mechanical polishing method using the same |
| KR101359092B1 (en) * | 2009-11-11 | 2014-02-05 | 가부시키가이샤 구라레 | Slurry for chemical mechanical polishing and polishing method for substrate using same |
-
2005
- 2005-07-04 JP JP2005195257A patent/JP2007013059A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101359092B1 (en) * | 2009-11-11 | 2014-02-05 | 가부시키가이샤 구라레 | Slurry for chemical mechanical polishing and polishing method for substrate using same |
| US9536752B2 (en) | 2009-11-11 | 2017-01-03 | Kuraray Co., Ltd. | Slurry for chemical mechanical polishing and polishing method for substrate using same |
| WO2011136387A1 (en) * | 2010-04-28 | 2011-11-03 | 株式会社バイコウスキージャパン | Sapphire polishing slurry and sapphire polishing method |
| JP2013043893A (en) * | 2011-08-22 | 2013-03-04 | Jsr Corp | Aqueous dispersion for chemical and mechanical polishing and chemical and mechanical polishing method using the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1306562C (en) | Polishing compound, method for production thereof, and polishing method | |
| JP6480381B2 (en) | Barrier chemical mechanical planarization slurry using ceria-coated silica abrasive | |
| JP4075985B2 (en) | Polishing composition and polishing method using the same | |
| US7037351B2 (en) | Non-polymeric organic particles for chemical mechanical planarization | |
| JP4952584B2 (en) | Polishing liquid for metal and polishing method of film to be polished | |
| KR101069472B1 (en) | Method for chemical mechanical planarization of chalcogenide materials | |
| TW202007753A (en) | Tungsten chemical mechanical polishing for reduced oxide erosion | |
| KR102691792B1 (en) | Titanium Nitride-Silicon Nitride Nitride Inhibitors for High Selectivity in Chemical-Mechanical Polishing Applications | |
| US20080148652A1 (en) | Compositions for chemical mechanical planarization of copper | |
| JPWO2008132983A1 (en) | Abrasive composition and method for producing semiconductor integrated circuit device | |
| JP4206233B2 (en) | Abrasive and polishing method | |
| JP2009534834A (en) | CMP method for copper-containing substrates | |
| KR20070001994A (en) | Abrasives and Polishing Methods | |
| JP2005167219A (en) | Composition and method for barrier removal | |
| WO2009056491A1 (en) | Cmp slurry composition and process for planarizing copper containing surfaces provided with a diffusion barrier layer | |
| JP3849091B2 (en) | Aqueous dispersion for chemical mechanical polishing | |
| JP2010529672A (en) | Chemical mechanical polishing slurry composition for copper damascene process | |
| JP2005175218A (en) | Slurry for polishing copper wiring | |
| JP2007242839A (en) | Abrasive compound for metal chemical mechanical polishing | |
| JP5094112B2 (en) | Polishing liquid | |
| JP2010010717A (en) | Abrasive agent and polishing method | |
| JP5319968B2 (en) | Polishing composition for CMP | |
| JP2007013059A (en) | Polishing composition for cmp | |
| JP2006066874A (en) | Polishing composition for CMP and polishing method | |
| JP2007335531A (en) | Polishing composition for metal cmp |