KR101693237B1 - Slurry composition for tungsten polishing - Google Patents
Slurry composition for tungsten polishing Download PDFInfo
- Publication number
- KR101693237B1 KR101693237B1 KR1020150112432A KR20150112432A KR101693237B1 KR 101693237 B1 KR101693237 B1 KR 101693237B1 KR 1020150112432 A KR1020150112432 A KR 1020150112432A KR 20150112432 A KR20150112432 A KR 20150112432A KR 101693237 B1 KR101693237 B1 KR 101693237B1
- Authority
- KR
- South Korea
- Prior art keywords
- abrasive grains
- abrasive
- slurry composition
- tungsten
- polishing
- Prior art date
Links
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 71
- 239000010937 tungsten Substances 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000002002 slurry Substances 0.000 title claims abstract description 61
- 238000005498 polishing Methods 0.000 title claims description 82
- 239000002245 particle Substances 0.000 claims abstract description 45
- 239000006061 abrasive grain Substances 0.000 claims description 210
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 61
- 239000008119 colloidal silica Substances 0.000 claims description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 229910021645 metal ion Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- -1 iron (Fe) ions Chemical class 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 6
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 5
- 239000001230 potassium iodate Substances 0.000 claims description 5
- 235000006666 potassium iodate Nutrition 0.000 claims description 5
- 229940093930 potassium iodate Drugs 0.000 claims description 5
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 5
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 claims description 3
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims description 3
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 claims description 3
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 claims description 3
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 2
- YUUVAZCKXDQEIS-UHFFFAOYSA-N azanium;chlorite Chemical compound [NH4+].[O-]Cl=O YUUVAZCKXDQEIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 claims description 2
- 229960001841 potassium permanganate Drugs 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 235000002639 sodium chloride Nutrition 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 235000012431 wafers Nutrition 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007517 polishing process Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 238000012876 topography Methods 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 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000013313 FeNO test Methods 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910002803 Si-O-Fe Inorganic materials 0.000 description 1
- 229910002802 Si–O–Fe Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 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
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
The present invention relates to a slurry composition for tungsten polishing.
As the design rule of the product is reduced, the aspect ratio (depth / floor width) is rapidly increasing due to the narrow width and height of the structure, and the influence of the scratches generated in the conventional 50- It affects the process more than 2 times. As a result, the influence of the flatness as well as the scratches on the surface of the film was also sensitized. The most important factors to be considered in the polishing process are the amount of polishing and the quality of the polishing surface. Recently, as the semiconductor design rule is reduced, the importance of the quality of the polishing surface is maximized.
On the other hand, as the degree of integration of semiconductors has increased recently, a lower current leakage is required, and a high-permittivity dielectric and a metal gate structure have been devised to satisfy this demand. Aluminum has been widely used as a metal gate material in general. However, due to problems such as difficulty in complete deposition due to reduction in design rule and difficulty in polishing aluminum oxide having high hardness, much research has been conducted on using tungsten as a gate material have. However, as the material is changed from an aluminum gate to a tungsten gate, tungsten forms a topography due to the tungsten crystal grain size after deposition, which causes a short between the undesired metals, resulting in a reduction in semiconductor yield. In order to improve the polishing surface quality of such tungsten, i.e., to improve the flatness, polishing is essential for the next generation process. The slurry composition which is not improved in flatness causes tungsten over etch or unetch in the post-polishing process, resulting in a process failure or unstable operation of the device, thereby drastically lowering the semiconductor yield. In addition, since the conventional slurry compositions for tungsten polishing are optimized for the polishing rate and the selectivity ratio to the titanium and silicon oxide films, the slurry composition is designed to have a low flatness improvement characteristic.
An object of the present invention is to provide a tungsten polishing slurry composition which has a high polishing rate and is excellent in flatness, by polishing a tungsten film.
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.
The slurry composition for tungsten polishing according to one embodiment of the present invention comprises at least two kinds of abrasive grains among first abrasive grains, second abrasive grains and third abrasive grains, and the specific surface area of the abrasive grains satisfies the following conditional expression 1: < RTI ID = 0.0 >
[Conditional expression 1]
20 m 2 / g ≤ (T A × K A) + (T B × K B) + (T C × K C) ≤ 100 m 2 / g
(Wherein T A is one of the specific surface area, the T B is a specific surface area of the second abrasive grain, the T C is and the specific surface of the third abrasive grain, the T A, T B, T C of the first abrasive particles 0 may be, the K a is the content ratio, K B is the content ratio of the K C of the second abrasive particles of the first abrasive particles and the content ratio of the third abrasive grain, 0≤K a <1, 0 ≤K B <1, 0≤K C <satisfies 1).
The specific surface area of the first abrasive grains, the second abrasive grains or the third abrasive grains may be 10 m 2 / g to 120 m 2 / g, respectively.
The specific surface area of the first abrasive grains is 70 m 2 / g to 120 m 2 / g, the specific surface area of the second abrasive grains is 25 m 2 / g to 70 m 2 / g, The specific surface area may be 10 m 2 / g to 25 m 2 / g.
Wherein the content of the first abrasive grains is 10 wt% to 70 wt% of the total abrasive grains, the content of the second abrasive grains is 10 wt% to 70 wt% of the total abrasive grains, May be 10 wt% to 70 wt% of the total abrasive grains.
Wherein the two or more kinds of abrasive grains each independently include at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic or inorganic material, and a metal oxide in a colloidal state, , Ceria, zirconia, alumina, titania, barium titania, germania, manganese, and magnesia.
And a part of the abrasive grains may be replaced by metal ions.
The metal ion may have a tetrahedral coordination.
The metal ion may be at least one selected from the group consisting of Fe, Al, As, Ga, B, Ber, C, Cr, (Ti), vanadium (V), zinc (Zn), and zirconium (Zr), in addition to the elements selected from the group consisting of indium (In), magnesium (Mg), manganese Or at least one of them.
The abrasive particles may be colloidal silica, the metal ion may be iron (Fe) ions, and some of the surfaces of the colloidal silica abrasive grains may be substituted with iron (Fe) ions.
And ammonium iodide, ammonium persulfate, ammonium persulfate, tetramethylammonium chlorate, tetramethylammonium iodate, potassium iodate, potassium iodate, ammonium permanganate, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, tetramethylammonium chlorate, At least one oxidizing agent selected from the group consisting of tetramethylammonium, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, 4-methylmorpholine N-oxide, pyridine-N-oxide and urea hydrogen peroxide As shown in Fig.
The oxidizing agent may be 0.005 wt% to 5 wt% of the slurry composition for tungsten polishing.
The slurry composition for tungsten polishing may be one which polishes tungsten having a thickness of 1,000 A / min to 2,200 A / min.
The flatness of the surface of the tungsten-containing wafer using the slurry composition for tungsten polishing may be 5% or less.
The surface of the tungsten-containing wafer using the slurry composition for tungsten polishing may have a peak to valley (Rpv) value of 100 nm or less and a surface roughness of 10 nm or less.
The pH of the slurry composition for tungsten polishing may be in the range of 1 to 12.
The slurry composition for tungsten polishing according to the present invention can realize a high polishing rate for a tungsten film, shortening the polishing process time and providing excellent flatness. Surface defects such as erosion phenomenon, dishing phenomenon and formation of a residue of a metal layer on the surface of the object to be polished can be significantly lowered, thereby reducing metal shorts and erroneous defects Thereby enabling a next-generation high integration process.
1 is an infrared absorption spectrum (FT-IR) graph of Fe ion-substituted colloidal silica abrasive particles and general colloidal silica abrasive particles of the present invention.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, terms used in this specification are terms used to appropriately express the preferred embodiments of the present invention, which may vary depending on the user, the intention of the operator, or the practice of the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification. Like reference symbols in the drawings denote like elements.
Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.
Hereinafter, the slurry composition for tungsten polishing of the present invention will be specifically described with reference to examples and drawings. However, the present invention is not limited to these embodiments and drawings.
The slurry composition for tungsten polishing according to the present invention comprises at least two kinds of abrasive grains: first abrasive grains, second abrasive grains and third abrasive grains, wherein the specific surface area of the abrasive grains satisfies the following
[Conditional expression 1]
20 m 2 / g ≤ (T A × K A) + (T B × K B) + (T C × K C) ≤ 100 m 2 / g
(Wherein T A is one of the specific surface area, the T B is a specific surface area of the second abrasive grain, the T C is and the specific surface of the third abrasive grain, the T A, T B, T C of the first abrasive particles 0 may be, the K a is the content ratio, K B is the content ratio of the K C of the second abrasive particles of the first abrasive particles and the content ratio of the third abrasive grain, 0≤K a <1, 0 ≤K B <1, 0≤K C <satisfies 1).
The reason why one of T A , T B and T C can be 0 is that the specific surface area value of one of the first abrasive particle, the second abrasive particle and the third abrasive particle can be 0, Means that only particles having a surface area are added.
The sum of the content ratios of the respective abrasive grains satisfies K A + K B + K C = 1, and one of the K A , K B and K C may be 0. The fact that one of K A , K B and K C can be 0 means that the content ratio of one of the first abrasive grain, the second abrasive grain and the third abrasive grain can be 0, Is added.
The ratio of the specific surface area to the specific surface area of each of the first abrasive grains, the second abrasive grains and the third abrasive grains is set to (T A × K A ) + (T B × K B ) + (T C × K C ) The sum of the multiplied values may be from 20 m 2 / g to 100 m 2 / g. If the sum of the specific surface area of each of the first abrasive grains, the second abrasive grains and the third abrasive grains is less than 20 m 2 / g, the polishing rate may be increased during the polishing step, but scratches may occur. If it is larger than 100 m 2 / g, there is a problem that a sufficient polishing rate can not be obtained.
The slurry composition for tungsten polishing according to the present invention can realize a high polishing rate for a tungsten film, shortening the polishing process time and providing excellent flatness. By including two or more kinds of mixed abrasive grains, surface defects such as erosion phenomenon, dishing phenomenon, and formation of a residue of a metal layer on the surface of an object to be polished can be significantly lowered. As a result, metal shorts and erroneous defects can be reduced and a next-generation high integration process can be performed.
In the present specification, "two or more types of abrasive grains" describes two or three kinds of abrasive grains. However, the present invention is not limited to this, and may include four or more kinds of abrasive grains. When the two or more types of abrasive grains are two types of abrasive grains, the abrasive grains having different specific surface areas are mixed by controlling the calcination condition and / or the milling condition, so that the abrasive grains having a bimodal- Lt; / RTI > Or when the two or more types of abrasive grains are three kinds of abrasive grains, three types of abrasive grains having different specific surface areas may be mixed to have a particle size distribution showing three peaks.
Wherein the first abrasive grains have a primary particle size of 20 nm or more and less than 45 nm, a primary particle size of the second abrasive grains is 45 nm or more and less than 130 nm, nm. < / RTI >
The second abrasive grains have a secondary particle size of 30 nm or more and less than 100 nm, a secondary particle size of the second abrasive grains of 100 nm or more and less than 250 nm, and a secondary particle size of the third abrasive grains of 250 nm Or more and less than 500 nm.
The abrasive grains may be prepared by mixing the first abrasive grains and the second abrasive grains, or by mixing the first abrasive grains with the second abrasive grains, or by mixing the first abrasive grains with the second abrasive grains, The first abrasive grains and the third abrasive grains or the second abrasive grains and the third abrasive grains may be mixed to have a bimodal shape size distribution. Or the first abrasive grains, the second abrasive grains, and the third abrasive grains may be mixed to have a particle size distribution showing three peaks. The relatively large abrasive grains and the relatively small abrasive grains can be mixed to have better dispersibility and the effect of reducing the scratch on the wafer surface can be expected.
In one embodiment of the present invention, the specific surface area of the first abrasive grains, the second abrasive grains or the third abrasive grains may be 10 m 2 / g to 120 m 2 / g, respectively. If the specific surface area of the abrasive grains is less than 10 m 2 / g, there is a possibility of occurrence of scratches between the polishing processes, and if it is more than 120 m 2 / g, it may be difficult to obtain excellent flatness.
For example, the specific surface area of the first abrasive grains is 70 m 2 / g to 120 m 2 / g, the specific surface area of the second abrasive grains is 25 m 2 / g to 70 m 2 / g, May have a specific surface area of 10 m 2 / g to 25 m 2 / g, but the present invention is not limited thereto and may be a mixture of two or three kinds of abrasive grains having a specific surface area of 10 m 2 / g to 120 m 2 / g ≪ / RTI > in any case.
When two or more types of abrasive grains are mixed, abrasive grains having a relatively large specific surface area and abrasive grains having a relatively small specific surface area are mixed, and thus the polishing speed can be 1.5 times or more higher than that of a single abrasive grains Excellent dispersibility and excellent flatness on the wafer surface can be expected.
Wherein the content of the first abrasive grains is 10 wt% to 70 wt% of the total abrasive grains, the content of the second abrasive grains is 10 wt% to 70 wt% of the total abrasive grains, May be 10 wt% to 70 wt% of the total abrasive grains. If the content of the abrasive grains is less than 10% by weight, a sufficient polishing rate can not be obtained in the polishing step. If the abrasive grains content is more than 70% by weight, scratches may occur between the polishing steps.
The polishing and topographic improvement of the tungsten-containing wafer is related to the contact area between the abrasive particles and the tungsten-containing film, and the abrasive grains in which the first abrasive grains, the second abrasive grains and the third abrasive grains are mixed in the above- When used, topography improvement effect is excellent. Particularly, the content of the first abrasive grains, the second abrasive grains and the third abrasive grains is determined within a range of improving the dispersion stability by calculating the contact area between each abrasive grain and the tungsten-containing film according to the mixing ratio .
Wherein the two or more kinds of abrasive grains each independently include at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic or inorganic material, and a metal oxide in a colloidal state, , Ceria, zirconia, alumina, titania, barium titania, germania, manganese, and magnesia.
On the other hand, the two or more types of abrasive grains may include metal-substituted abrasive grains in which a part of the abrasive grains are substituted with metal ions, and at least one of the first abrasive grains, the second abrasive grains, Or more may be metal-substituted abrasive grains. A part of the abrasive grains may be up to 30% from the surface of the abrasive grains or from the surface to the center of the abrasive grains. Refers to a point where the length from the surface to the center of the abrasive grains is regarded as 100%. In the surface of the abrasive grains, the metal ion may be one in which the component of the abrasive grains is replaced with the metal ion have.
The metal ion may have a tetrahedral coordination. The metal ion may be at least one selected from the group consisting of Fe, Al, As, Ga, B, Ber, C, Cr, (Ti), vanadium (V), zinc (Zn), and zirconium (Zr), in addition to the elements selected from the group consisting of indium (In), magnesium (Mg), manganese Or at least one of them.
The two or more kinds of abrasive grains may be colloidal silica, the metal ion may be iron (Fe) ion, and some of the surfaces of the colloidal silica abrasive grains may be substituted with iron (Fe) ions.
The metal-substituted abrasive particles may have a zeta potential of -10 mV to -70 mV at a pH of 1 to 12 at a zeta potential of -1 mV to -100 mV, preferably at a pH of 1 to 6. An absolute value of the zeta potential is also exhibited in the acidic region, whereby the dispersion stability is high and an excellent polishing force can be realized.
The method for producing the metal-substituted abrasive particles comprises: preparing a mixture by mixing abrasive particles with a metal salt, a metal ion compound, or both; And synthesizing the mixture under hydrothermal synthesis conditions. And substitutes the metal oxide element and metal ion of the abrasive particles by the property that the metal ion has a tetrahedral coordination in an alkali condition.
The metal salt may be at least one selected from the group consisting of Fe, Al, As, Ga, B, Ber, Cb, Cr, Hf, At least one selected from the group consisting of In, Mg, Mn, Ni, P, Ti, V, Zn and Zr, Or a salt of any one of the metals. As a salt of iron of the metal salt, iron nitrate (Fe (NO 3) 3, ferric nitrate), iron sulfate (Fe 2 (SO 4) 3 , ferric sulfate), iron oxide (Fe 2 O 3, ferric oxide) and iron ( FeCl 3 , and ferric chloride. In the case of iron nitrate, it is dissociated from water to provide iron ions (Fe 2+ , Fe 3 ).
The metal ion compound is selected from the group consisting of sodium nitrate, lithium nitrate, potassium nitrate, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium sulfate, lithium sulfate, potassium sulfate, sodium chloride, lithium chloride, potassium chloride, lithium carbonate and potassium carbonate And may include at least any one selected.
The metal salt may be 0.001 to 20 parts by weight based on 100 parts by weight of the abrasive grains. When the amount of the metal salt is less than 0.001 part by weight, it is difficult to obtain sufficient zeta charge and dispersion stability is poor. When the amount of the metal salt exceeds 20 parts by weight, there is a possibility that the unreacted metal salt may cause a contamination problem.
The metal ion compound may be 0.001 to 20 parts by weight based on 100 parts by weight of the abrasive grains. If the amount of the metal ion compound is less than 0.001 part by weight, the metal ion may not be smoothly substituted. If the amount of the metal ion compound exceeds 20 parts by weight, a problem of contamination may occur and a dispersion stability may be deteriorated Can be.
The step of synthesizing the mixture under the hydrothermal synthesis condition, which is carried out in order to proceed the metal substitution reaction efficiently, may be a hydrothermal synthesis in a temperature range of 100 ° C to 300 ° C for 0.5 hours to 72 hours.
The pH of the mixture may be adjusted to 9 to 12 before proceeding with the hydrothermal synthesis, and the pH may be adjusted to 1 to 5 after the hydrothermal synthesis is completed. The pH adjusting agent used herein may be an acid or base without limitation and may be any one of potassium hydroxide, sodium hydroxide, ammonia, ammonia derivatives, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, boric acid, amino acid, citric acid, tartaric acid, formic acid, Oxalic acid, tartaric acid, and acetic acid may be used to prepare metal-substituted abrasive grains in an amount such that the desired pH can be adjusted.
The metal ion is not simply bonded to the surface of the metal-substituted abrasive grains, but the metal ion having the tetrahedral coordination in the alkali region is used, And the surface is modified by replacing the metal ion, whereby the dispersion stability is high even in the acidic region. In addition, the metal oxide element ion and the substituted metal ion on the surface of the abrasive grains can promote the oxidation of the metal film, thereby realizing a high polishing characteristic capable of easily polishing the tungsten film.
The shape of each of the first abrasive grains, the second abrasive grains and the third abrasive grains may be at least one selected from the group consisting of spherical, angular, acicular, and plate- .
The slurry composition for tungsten polishing according to the present invention may contain at least one selected from the group consisting of hydrogen peroxide, ferric nitrate, potassium iodate, potassium permanganate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium periodate, ammonium tetrachloride Methylmorpholine N-oxide, pyridine-N-oxide, and urea hydrogen peroxide, in a solvent selected from the group consisting of methyl ammonium, tetramethylammonium chlorate, tetramethylammonium iodide, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, And at least one oxidizing agent selected from the group consisting of Among them, it is preferable to use hydrogen peroxide in view of the oxidative power and the dispersion stability of the slurry composition for tungsten polishing and economical efficiency.
The oxidizing agent may be 0.005 wt% to 5 wt%, preferably 0.05 wt% to 1 wt% of the slurry composition for tungsten polishing. When the oxidizing agent is less than 0.005 wt% in the polishing slurry composition, the polishing rate and the etching rate with respect to tungsten may be lowered. When the oxidizing agent is more than 5 wt%, the oxide film on the tungsten surface becomes hard, The oxide film grows, and the topography can be deteriorated due to corrosion and aging of tungsten. Since the oxidizing agent directly affects the polishing rate and the etching rate of tungsten, it is necessary to reduce the concentration of hydrogen peroxide in the present invention, which considers the quality of the tungsten surface.
The slurry composition for tungsten polishing according to the present invention may further include a material used for preventing corrosion of a metal or a polishing machine and for realizing a pH range in which metal oxidation easily occurs. The pH adjusting agent may be an inorganic acid or an inorganic acid salt including at least one selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, bromic acid, iodic acid and salts thereof; And organic acids such as formic acid, malonic acid, maleic acid, oxalic acid, acetic acid, citric acid, adipic acid, acetic acid, propionic acid, fumaric acid, lactic acid, salicylic acid, pimelic acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, An organic acid or an organic acid salt containing at least one selected from the group consisting of glycolic acid, lactic acid, aspartic acid, tartaric acid and salts thereof.
The slurry composition for tungsten polishing may be one which polishes tungsten having a thickness of 1,000 A / min to 2,200 A / min.
The flatness of the surface of the tungsten-containing wafer using the slurry composition for tungsten polishing may be 5% or less. Examples of the tungsten-containing wafers include tungsten, tantalum, titanium, ruthenium, hafnium, other refractory metals, nitrides and silicides thereof.
The surface of the tungsten-containing wafer using the slurry composition for tungsten polishing may have a peak to valley (Rpv) value of 100 nm or less and a surface roughness of 10 nm or less. The peak-to-valley value can be measured with an atomic force microscope.
The pH of the slurry composition for tungsten polishing according to the present invention is preferably adjusted to provide dispersion stability and proper polishing rate depending on the abrasive grain, and the pH of the slurry composition for tungsten polishing is 1 to 12, preferably 1 to 6 It may be one having an acidic pH range.
Hereinafter, the present invention will be described in detail with reference to the following examples and comparative examples. However, the technical idea of the present invention is not limited or limited thereto.
[Example 1]
Two kinds of abrasive grains were mixed at a ratio of 50% of the first abrasive grains of colloidal silica (Fuso Chemical Co.) and 50% of the second abrasive grains of colloidal silica to obtain abrasive grains having a total specific surface area of 69.9089 m 2 / g 3 parts by weight of a slurry composition, 0.5 parts by weight of hydrogen peroxide as an oxidizing agent, 0.1 parts by weight of malonic acid as a reaction inhibitor and nitric acid as a pH adjusting agent were added to prepare a polishing slurry composition having a pH of 2.5.
[Example 2]
Except that abrasive grains having a specific surface area of 55.2498 m 2 / g were used as a mixture of two kinds of abrasive grains in a ratio of 50% of colloidal silica first abrasive grains and 50% of colloidal silica third abrasive grains. 1 < / RTI > to prepare a polishing slurry composition.
[Example 3]
Except that abrasive grains having a specific surface area of 29.4898 m 2 / g were used as a mixture of two abrasive grains in a ratio of 50% colloidal silica second abrasive grains and 50% colloidal silica third abrasive grains. 1 < / RTI > to prepare a polishing slurry composition.
[Example 4]
Three types of abrasive grains were mixed at a ratio of 40% of colloidal silica first abrasive grains, 40% of colloidal silica second abrasive grains and 40% of colloidal silica third abrasive grains, and the sum of specific surface areas was 58.8933 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.
[Example 5]
Three kinds of abrasive grains were mixed at a ratio of 40% of colloidal silica first abrasive grains, 20% of colloidal silica second abrasive grains and 40% of colloidal silica third abrasive grains, and the sum of specific surface areas was 53.0296 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.
[Example 6]
Three kinds of abrasive grains were mixed at a ratio of 20% of colloidal silica first abrasive grains, 40% of colloidal silica second abrasive grains and 40% of colloidal silica third abrasive grains, and the sum of specific surface areas was 42.7256 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.
[Example 7]
Three kinds of abrasive grains were mixed at a ratio of 40% of colloidal silica first abrasive grains, 30% of colloidal silica second abrasive grains and 30% of colloidal silica third abrasive grains, and the sum of specific surface areas was 55.9614 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.
[Example 8]
Three kinds of abrasive grains were mixed at a ratio of 30% of colloidal silica first abrasive grains, 40% of colloidal silica second abrasive grains and 30% of colloidal silica third abrasive grains, and the sum of specific surface areas was 50.8094 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.
[Example 9]
Three types of abrasive grains were mixed at a ratio of 30% of colloidal silica first abrasive grains, 30% of colloidal silica second abrasive grains and 40% of colloidal silica third abrasive grains, and the sum of specific surface areas was 47.8776 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.
[Example 10]
Three kinds of abrasive grains were mixed at a ratio of 33% of colloidal silica first abrasive grains, 33% of colloidal silica second abrasive grains and 34% of colloidal silica third abrasive grains, and the sum of specific surface areas was 51.0340 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.
[Example 11]
As the colloidal silica abrasive grains, Fe ion-substituted colloidal silica abrasive grains were used. The method for producing the Fe ion-substituted colloidal silica abrasive particles was such that 5 wt% of colloidal silica abrasive grains, 0.17 wt% of iron nitrate ((FeNO 3 ) 3 ) and 0.484 wt% of sodium nitrate (NaNO 3 ) The mixed solution was prepared and titrated with sodium hydroxide (NaOH) until the pH reached 11. The mixed solution containing colloidal silica with controlled pH was placed in a hydrothermal reactor and subjected to hydrothermal reaction at 140 for 24 hours to prepare Fe ion-substituted colloidal silica abrasive particles.
In order to confirm the Fe ion substitution of the Fe ion-substituted colloidal silica abrasive particles, the Fe ion-substituted colloidal silica abrasive particles were centrifuged and the cake was dried at 110 to 24 hours. KBr Pellets were prepared by mixing and measured with an infrared spectroscope. 1 is an infrared absorption spectrum (FT-IR) graph of Fe ion-substituted colloidal silica abrasive particles and general colloidal silica abrasive particles of the present invention. The horizontal axis represents the wave number and the vertical axis represents the transmittance. Referring to FIG. 1, a Si-O-Fe bonding peak can be confirmed at 668 cm -1 . This analysis shows that the Fe-substitution is well done.
In a ratio of 40% of the Fe ion-substituted colloidal silica first abrasive grains, 20% of the Fe ion-substituted colloidal silica second abrasive grains and 40% of the Fe ion-substituted colloidal silica third abrasive grains, Of abrasive grains were mixed to prepare a polishing slurry composition under the same conditions as in Example 1, except that abrasive grains having a specific surface area of 58.8933 m 2 / g were used.
[Example 12]
In the ratio of 30% of the Fe ion-substituted colloidal silica first abrasive grains, 40% of the Fe ion-substituted colloidal silica second abrasive grains and 30% of the Fe ion-substituted colloidal silica third abrasive grains, Were mixed to prepare a polishing slurry composition under the same conditions as in Example 1, except that abrasive grains having a specific surface area of 50.8094 m 2 / g were used.
[Comparative Example 1]
The polishing slurry composition was prepared under the same conditions as in Example 1, except that only the first abrasive grains of colloidal silica having a specific surface area of 95.6689 m 2 / g were used.
[Comparative Example 2]
The polishing slurry composition was prepared under the same conditions as in Example 1 except that only the second abrasive grains of colloidal silica having a specific surface area of 44.1489 m 2 / g were used.
[Comparative Example 3]
A polishing slurry composition was prepared under the same conditions as in Example 1 except that only the third abrasive grains of colloidal silica having a specific surface area of 14.8307 m 2 / g were used.
The polishing slurry compositions of Examples 1 to 12 and Comparative Examples 1 to 3 of the present invention were used to polish a tungsten wafer under the following polishing conditions.
[Polishing condition]
1. Polishing equipment: Bruker's CETR CP-4
2. Wafer: 6 cm x 6 cm tungsten wafer
3. Platen pressure: 3 psi
4. Spindle speed: 69 rpm
5. Platen speed: 70 rpm
6. Flow rate: 100 ml / min
7. Slurry solids content: 3 wt%
Table 1 below shows the abrasive grain content, specific surface area, tungsten polishing rate and flatness after polishing of tungsten wafers using the respective slurry compositions in the slurry compositions of Examples 1 to 12 and Comparative Examples 1 to 3 of the present invention will be.
Abrasive particle
(%)
Abrasive particle
(%)
Abrasive particle
(%)
(m 2 / g)
Abrasion rate
(Å / min)
Examples 1 to 3, which contained two or more types of abrasive grains in Examples 1 to 12 and Comparative Examples 1 to 3 of the present invention and had a specific surface area value of mostly 20 m 2 / g or more and 70 m 2 / g or less It can be seen that the tungsten polishing slurry composition of the present invention has a larger tungsten polishing rate than that of the slurry compositions of Comparative Examples 1 to 3 which are slurry compositions for tungsten polishing including single species of specific surface polishing particles, Value of 5% or less. In particular, in Examples 11 and 12 using three kinds of Fe ion-substituted silica abrasive grains, it can be seen that the tungsten polishing rate is high.
As a result, it was found that the use of the slurry composition for tungsten polishing mixed with two or three kinds of silica particles resulted in a higher tungsten polishing rate and improved flatness compared to the polishing slurry composition containing colloidal silica particles having a single composition have.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible. Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the equivalents of the appended claims, as well as the appended claims.
Claims (15)
Wherein the specific surface area of the first abrasive grains, the second abrasive grains or the third abrasive grains satisfies the following conditional expression 1 within a range of 10 m 2 / g to 120 m 2 / g, respectively: Composition:
[Conditional expression 1]
20 m 2 / g ≤ (T A × K A) + (T B × K B) + (T C × K C) ≤ 100 m 2 / g
(Wherein T A is one of the specific surface area, the T B is a specific surface area of the second abrasive grain, the T C is and the specific surface of the third abrasive grain, the T A, T B, T C of the first abrasive particles 0 may be, the K a is the content ratio, K B is the content ratio of the K C of the second abrasive particles of the first abrasive particles and the content ratio of the third abrasive grain, 0≤K a <1, 0 ≤K B <1, 0≤K C <satisfies 1).
The specific surface area of the first abrasive grains is 70 m 2 / g to 120 m 2 / g,
The specific surface area of the second abrasive grains is 25 m 2 / g to 70 m 2 / g,
And the specific surface area of the third abrasive grains is 10 m 2 / g to 25 m 2 / g.
The content of the first abrasive grains is 10 wt% to 70 wt% of the total abrasive grains,
The content of the second abrasive grains is 10 wt% to 70 wt% of the total abrasive grains,
Wherein the content of the third abrasive grains is 10 wt% to 70 wt% of the total abrasive grains.
The two or more kinds of abrasive grains are, independently of each other,
At least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic or inorganic material, and a metal oxide in a colloidal state,
Wherein the metal oxide comprises at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, manganese, and magnesia.
Wherein the abrasive grains have a component part of the abrasive grains substituted with metal ions.
Wherein the metal ion has a tetrahedral coordination.
The metal ion may be at least one selected from the group consisting of Fe, Al, As, Ga, B, Ber, C, Cr, (Ti), vanadium (V), zinc (Zn), and zirconium (Zr), in addition to the elements selected from the group consisting of indium (In), magnesium (Mg), manganese And at least one of them is contained.
Wherein the abrasive grains are colloidal silica and the metal ions are iron (Fe) ions, wherein some of the surfaces of each of the colloidal silica abrasive grains are substituted with iron (Fe) ions. Composition.
And ammonium persulfate, ammonium persulfate, tetramethylammonium chlorate, tetramethylammonium iodate, potassium iodate, potassium iodate, potassium permanganate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, tetramethylammonium chlorate, At least one oxidizing agent selected from the group consisting of tetramethylammonium, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, 4-methylmorpholine N-oxide, pyridine-N-oxide and urea hydrogen peroxide Further comprising a slurry composition for tungsten polishing.
Wherein the oxidizing agent is 0.005 wt% to 5 wt% of the slurry composition for tungsten polishing.
Wherein the slurry composition for tungsten polishing is a tungsten polishing slurry composition having a thickness of 1,000 A / min to 2,200 A / min.
Wherein the flatness of the surface of the tungsten-containing wafer using the slurry composition for tungsten polishing is 5% or less after polishing.
Wherein the surface of the tungsten-containing wafer using the slurry composition for tungsten polishing has a peak to valley (Rpv) value of 100 nm or less and a surface roughness of 10 nm or less. .
Wherein the pH of the slurry composition for tungsten polishing is in the range of 1 to 12. 5. The tungsten polishing slurry composition according to claim 1,
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US15/205,684 US10077381B2 (en) | 2015-07-20 | 2016-07-08 | Polishing slurry composition |
CN201610575493.0A CN106366934B (en) | 2015-07-23 | 2016-07-19 | Polishing material paste composition |
TW106115948A TWI633163B (en) | 2015-07-23 | 2016-07-19 | Polishing slurry composition |
TW105122690A TWI609057B (en) | 2015-07-23 | 2016-07-19 | Polishing slurry composition |
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KR20120134105A (en) * | 2010-02-01 | 2012-12-11 | 제이에스알 가부시끼가이샤 | Aqueous dispersion for chemical mechanical polishing, and chemical mechanical polishing method using same |
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KR20120134105A (en) * | 2010-02-01 | 2012-12-11 | 제이에스알 가부시끼가이샤 | Aqueous dispersion for chemical mechanical polishing, and chemical mechanical polishing method using same |
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