TWI546371B - 研磨組成物 - Google Patents
研磨組成物 Download PDFInfo
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- TWI546371B TWI546371B TW103138930A TW103138930A TWI546371B TW I546371 B TWI546371 B TW I546371B TW 103138930 A TW103138930 A TW 103138930A TW 103138930 A TW103138930 A TW 103138930A TW I546371 B TWI546371 B TW I546371B
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- Prior art keywords
- ruthenium
- weight
- substrate
- sodium
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- 238000005498 polishing Methods 0.000 title claims description 53
- 239000000203 mixture Substances 0.000 title claims description 43
- 239000002002 slurry Substances 0.000 title 1
- 239000000758 substrate Substances 0.000 claims description 50
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 37
- 229910052707 ruthenium Inorganic materials 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 22
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 21
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 18
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 125000000129 anionic group Chemical group 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 16
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 14
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 229910052811 halogen oxide Inorganic materials 0.000 claims description 7
- 235000003270 potassium fluoride Nutrition 0.000 claims description 7
- 239000011698 potassium fluoride Substances 0.000 claims description 7
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000929 Ru alloy Inorganic materials 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 4
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 4
- 239000001230 potassium iodate Substances 0.000 claims description 4
- 235000006666 potassium iodate Nutrition 0.000 claims description 4
- 229940093930 potassium iodate Drugs 0.000 claims description 4
- CUNPJFGIODEJLQ-UHFFFAOYSA-M potassium;2,2,2-trifluoroacetate Chemical compound [K+].[O-]C(=O)C(F)(F)F CUNPJFGIODEJLQ-UHFFFAOYSA-M 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 claims description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 4
- 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 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims 1
- 229940005991 chloric acid Drugs 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910008045 Si-Si Inorganic materials 0.000 description 3
- 229910006411 Si—Si Inorganic materials 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910013627 M-Si Inorganic materials 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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
- -1 amine compounds Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Chemical compound O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- OMPIYDSYGYKWSG-UHFFFAOYSA-N Citronensaeure-alpha-aethylester Natural products CCOC(=O)CC(O)(C(O)=O)CC(O)=O OMPIYDSYGYKWSG-UHFFFAOYSA-N 0.000 description 1
- 229910008284 Si—F Inorganic materials 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229940057975 ethyl citrate Drugs 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 208000010727 head pressing Diseases 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000007521 mechanical polishing technique Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
-
- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
Description
本發明涉及一種化學機械研磨液,特別是一種用於矽鍺合金基材的研磨組成物。
目前半導體的製程已進入至16/14奈米的階段,即將進入10奈米以下節點,採用立體結構的電晶體,例如:搭配III-V族及鍺(Ge)做為通道材料的鰭式場效電晶體(FinFET)。由於III-V族半導體晶圓材料可提供較矽高出十到三十倍的電子遷移率(Electron Mobility),鍺可提供較矽高出四倍以上的電洞遷移率,因此便可有效控管電晶體閘極漏電流問題,提高電子移動率,可大幅提升晶片運算效能並同時降低功耗。故,III-V族材料化合物,尤其是矽鍺與鍺等之應用備受期待。
在次微米半導體製程中,通常藉由化學機械拋光(chemical mechanical polishing,CMP)來達到晶圓表面之平坦化(global planarization)。然而,在金屬化學機械研磨之技術中,在金屬層表面仍然常常發生金屬碟陷(Dishing)、磨蝕(Erosion)及腐蝕(corrosion)等研磨缺陷。若要對上述以矽鍺為鰭式場效電晶體主材料進行化學機械拋光,例如:在美國專利US 2011/0291188 A1和US 2012/0168913 A1所描述的FinFET結構,則會同時研磨到矽、矽鍺、與二氧化矽基材,因此會對上述三種基材的移除比有所限制。
在美國專利US2012/0190210 A1中揭示目前用於含矽基材的研磨液多半使用帶有強烈異味的乙二胺或其他胺類化合物或是對人體接觸有高危險性的氫氟酸。鑑此,有必要開發一種不具異味及氫氟酸,並且可有效提升含矽基材的移除速率且不對研磨對象造成嚴重腐蝕的研磨組成物。
請參考表一,表一為一比較表,採用雙氧水(過氧化氫)與乙二胺調製而成的研磨組成物對矽鍺基材(該矽鍺基材中鍺的含量為10%至80%)、矽基材與二氧化矽基材等進行化學機械拋光,其中該雙氧水作為氧化劑使用,而乙二胺則具有催化劑的功能。一般研磨應用時,氧化劑是用於使金屬產生易於被移除的金屬氧化物、抑制劑是用於阻擋氧化反應、催化劑是用於促進金屬移除、界面活性劑是用於避免研磨顆粒聚集並產生潤滑效果以減少刮傷缺陷的產生、以及緩衝劑是用於保持pH穩定。
使用上述研磨組成物的拋光條件如下:拋光機:Mirra 8”Polish;拋光墊:IC1010;清洗液:去離子水;晶圓:矽鍺控片、TEOS(Tetraethylortho silicate,矽酸乙酯)控片、裸矽控片;拋光時間:1分鐘;研磨頭下壓壓力:1.5psi;研磨頭轉速:73/67rpm。
上表一中,矽鍺基材的靜態蝕刻率(Static Etching Rate,SER)是以將3cm x 3cm之矽鍺基材置入研磨組成物中靜置5分鐘,採用重量差的方式計算而得。由表一比較例1-4的數據顯示,採用雙氧水作為氧化劑可得到大於2000埃/min的矽鍺移除速率(Removal Rate,R.R.),但是靜態蝕刻速率卻將近500埃/min,因為會對上述基材的表面造成腐蝕。此外,加入乙二胺催化劑對矽的移除速率的提昇也有限。可見以雙氧水為氧化劑的系統並無法有效控制各基材的移除比以及靜態蝕刻率。
為達上揭目的,本發明提供一種研磨組成物,適用於矽鍺合金基材之研磨,包含:研磨顆粒;具有六價鉬或五價釩之化合物,用於直接對該矽鍺合金基材進行催化和氧化反應;以及載劑,其中該研磨顆粒的含量為0.01wt%至5wt%,該具有六價鉬或五價釩之化合物的含量為0.01wt%至1.0wt%。
根據本發明的一實施例所述,在上述研磨組成物中還可包含有一陰離子添加物,其中該陰離子添加物的含量為0.01wt%至1.0wt%。
根據本發明的另一實施例所述,在上述研磨組成物中還可包
含有一含鹵素氧化物之化合物或其鹽類,其中該鹵素氧化物之化合物或其鹽類的含量為0.05wt%至5wt%。
根據本發明的一實施例所述,在上述研磨組成物中,該研磨顆粒為選自膠體二氧化矽或燻製二氧化矽。
根據本發明的一實施例所述,在上述研磨組成物中,該具有六價鉬或五價釩之化合物為選自三氧化鉬、鉬酸、磷鉬酸、五氧化二釩、偏釩酸鈉與釩酸鈉等所組成的族群中的至少一者。
根據本發明的一實施例所述,在上述研磨組成物中,該陰離子添加物為選自氟化鉀,氟化鈉、氟化銨、三氟醋酸、三氟醋酸鉀、三氟醋酸鈉等所組成的族群中的至少一者。
根據本發明的一實施例所述,在上述研磨組成物中,該含鹵素氧化物之化合物或其鹽類為選自過碘酸鉀、碘酸鉀、過氯酸鉀、過氯酸鈉、氯酸鉀,氯酸鈉、次氯酸鈉等所組成的族群中的至少一者。
根據本發明的一實施例所述,在上述研磨組成物中,該載劑包括水。
根據本發明的一實施例所述,在上述研磨組成物中,該研磨組成物之pH值範圍為7至12。
根據本發明的一實施例,所述研磨組成物係用於對矽鍺基材,矽基材與二氧化矽基材進行化學機械拋光。且在該矽鍺基材中鍺的含量為10%至80%。
根據本發明的上述實施例,其中該矽鍺基材的靜態蝕刻速率為0埃/分鐘。
為讓本發明之上述特徵和優點能更明顯易懂,下文特舉實施例作詳細說明如下。本發明之專利範圍並不侷限於該些實施例,應由申請專利範圍所定義。
本發明提供一種研磨組成物,其包括:研磨顆粒;具有六價鉬或五價釩之化合物;以及載劑。上述該研磨顆粒是研磨液組成的一個主要成分,其對於材料移除率及其表面品質有較直接的影響。在半導體製程中,常見的研磨顆粒為二氧化矽(SiO2)以及氧化鋁(Al2O3)等,其中二氧化矽研磨顆粒又可區分為膠體二氧化矽(colloidal)以及燻製二氧化矽(fumed),由於氧化鋁研磨顆粒通常具有較高的硬度,容易在平坦化製程後造成金屬導線的缺陷及刮傷。因此,在本發明的實施例中所述研磨顆粒選自為膠體二氧化矽或燻製二氧化矽。另一方面,研磨顆粒的濃度也是影響晶圓拋光的重要因素,若研磨顆粒濃度過高會加速機械研磨的效應,容易產生表面磨蝕之研磨缺陷以及過高的二氧化矽移除率導致選擇比降低;若濃度過低,則無法達到所期望之研磨去除率。因此在本發明一實例中,該研磨顆粒可以0.01wt%至5wt%之濃度存在於該載劑中,該載劑可為去離子水或其他包含水的溶液。
上述該具有六價鉬或五價釩之化合物(M)具有氧化能力,其會插入矽基材中的Si-Si鍵進行化學反應(insertion),形成Si-M-Si的型態,將Si-Si鍵打斷,之後,再藉由其本身的氧化能力使Si-M-Si型態氧化成SiO2,
達到移除的目的。由於上述將Si-Si鍵打斷的反應為速率決定步驟(rate determine step)因此該具有六價鉬或五價釩之化合物亦可稱為金屬催化劑用以提升基材之間的移除率與選擇性。其可選自為,但非限於三氧化鉬、鉬酸、磷鉬酸、五氧化二釩、偏釩酸鈉與釩酸鈉等所組成的族群中的至少一者,且其含量相對於該載劑的重量百分比濃度可優選為0.01wt%至1.0wt%。
請參考下表二,表二為本發明利用上述研磨組成物對矽鍺基材(鍺的含量為10%至80%)、矽基材與二氧化矽基材進行化學機械拋光的具體實施例。其拋光條件與上述比較例相同,在此不再贅述。
由表二實施例1-9的數據顯示,在鹼性環境下,將作為催化劑的五氧化二釩(五價釩)調配於100~10000ppm的濃度範圍下可以提升矽的移除速率,並且少量提升矽鍺的移除速率,但是隨著劑量的提高,矽鍺和矽的移除速率增加的幅度會變緩,而對於二氧化矽的移除速率無顯著影響。從實施例10-17的數據顯示,在鹼性環境下,將作為催化劑的三氧化鉬(六價鉬)調配於100~10000ppm的濃度範圍下可以提升矽的移除速率,並且少量提升矽鍺的移除速率。上述的鹼性環境具體為將pH值調控於7至12的範圍內。
由此可見,相對於比較例1-4,本發明研磨組成物中所添加之具有六價鉬或五價釩之化合物可大幅提升矽的移除率,同時提高矽鍺與矽相對於二氧化矽之選擇性。
在本發明另一實施例中,所述研磨組成物也可包含:研磨顆粒;陰離子添加物;以及載劑。其中該研磨顆粒可選自膠體二氧化矽或燻
製二氧化矽,其含量相對於該載劑(例如:去離子水或其他包含水的溶液)的重量百分比濃度可優選為0.01wt%至5wt%;該陰離子添加物可選自為,但非限於氟化鉀,氟化鈉、氟化銨、三氟醋酸、三氟醋酸鉀、三氟醋酸鈉等所組成的族群中的至少一者,且其含量相對於該載劑的重量百分比濃度可優選為0.01wt%至1.0wt%。
請參考下表三,表三為本發明利用上述研磨組成物對矽鍺基材(鍺的含量為10%至80%)、矽基材與二氧化矽基材進行化學機械拋光的具體實施例,其拋光條件與上述比較例相同,在此不再贅述。
該陰離子添加物和矽有很強的作用力,例如在表三中所列舉的氟離子可與矽生成強烈的Si-F鍵,因此可進一步協助Si-Si斷鍵而達到移除的目的。由表三實施例18-25的數據顯示,在鹼性環境下,將作為陰離子添
加物的氟離子或三氟醋酸根離子調配於100~10000ppm的濃度範圍下可少量提昇矽和矽鍺的移除速率,對於二氧化矽的移除速率則較無顯著影響。
綜合上述實施例1-25的數據顯示,具有六價鉬或五價釩之化合物和陰離子添加物可提升矽和矽鍺的移除率,但是再提高到更高的劑量時提升矽和矽鍺的移除速率逐漸趨緩。
在本發明的另一實施例中,上述研磨組成物除了研磨顆粒以及載劑之外也可同時包含具有六價鉬或五價釩之化合物以及一陰離子添加物。其中該矽研磨顆粒可選自膠體二氧化矽或燻製二氧化矽,其含量相對於該載劑(例如:去離子水或其他包含水的溶液)的重量百分比濃度可優選為0.01wt%至5wt%;該具有六價鉬或五價釩之化合物可選自為,但非限於三氧化鉬、鉬酸、磷鉬酸、五氧化二釩、偏釩酸鈉與釩酸鈉等所組成的族群中的至少一者;該陰離子添加物可選自為,但非限於氟化鉀,氟化鈉、氟化銨、三氟醋酸、三氟醋酸鉀、三氟醋酸鈉等所組成的族群中的至少一者。上述具有六價鉬或五價釩之化合物以及一陰離子添加物的濃度相對於該載劑的重量百分比濃度較皆可選自為0.01wt%至1.0wt%。
請參考下表四,表四為本發明利用上述研磨組成物對矽鍺基材(鍺的含量為10%至80%)、矽基材與二氧化矽基材進行化學機械拋光的具體實施例,其拋光條件與上述比較例相同,在此不再贅述。
由表四實施例26-35的數據顯示,將1500ppm的五氧化二釩或三氧化鉬(金屬催化劑)與100~10000ppm的氟化鉀或2000ppm三氟醋酸(陰離子添加物)混合後,在鹼性環境下,可再進一步提高矽和矽鍺的移除率,對於二氧化矽的移除率則較無明顯影響。由表中結果得知隨著五氧化二釩與氟化鉀劑量的提高,矽鍺和矽的移除速率增加的幅度會變緩,對於二氧化矽的移除速率則較無顯著影響。
由於在上述表四中矽鍺的移除率仍然偏低,因此,於本發明的另一實施例中,上述研磨組成物除了研磨顆粒、載劑、六價鉬或五價釩之化合物以及一陰離子添加物之外還可進一步包含有一鹵素氧化物之化合物或其鹽類。其中該鹵素氧化物之化合物或其鹽類具有氧化劑之功效,且可選自為,但非限於過碘酸鉀、碘酸鉀、過氯酸鉀、過氯酸鈉、氯酸鉀,氯酸鈉、次氯酸鈉等所組成的族群中的至少一者,且其濃度相對於該載劑
的重量百分比濃度可選自為0.05wt%至5wt%。
請參考下表五,表五為本發明利用上述研磨組成物對矽鍺基材、矽基材與二氧化矽基材進行化學機械拋光的具體實施例,其拋光條件與上述比較例相同,在此不再贅述。
實施例36-53係將做為氧化劑的碘酸鉀或次氯酸鈉以500~50000ppm的濃度混入濃度為1500ppm的五氧化二釩或三氧化鉬(金屬催化劑)和濃度為2000ppm的氟化鉀(陰離子添加物)之溶液中。數據顯示該氧化劑的加入可再提升矽的移除速率,並大幅提升矽鍺的移除率,且靜態蝕刻率為0,而在pH 7~12間研磨數據也接近。實施例42-44與51-53數據顯示提高研磨粒含量也會提高矽鍺、矽與二氧化矽的研磨率。
綜合上述比較例與實施例的數據可得知:含鹵素氧化物之氧化劑可氧化矽與矽鍺基材,使其基材表面形成氧化層以利提升移除速率,在陰離子添加物和具六價鉬或五價釩之化合物的存在下可彈性調整矽、矽鍺與二氧化矽基材的移除比。例如在實施例31中,矽對二氧化矽選擇比分別為60:1;矽鍺與二氧化矽選擇比為45:1;矽與矽鍺選擇比為1.3:1。本發明的研磨組成物具有矽鍺基材對二氧化矽基材的高選擇比、矽基材對二氧化矽基材的高選擇比,且該選擇比可依需求調整,因此可視為例如以矽鍺為主材料的鰭式場效電晶體之研磨需求。
本發明的研磨組成物在矽與矽鍺基材移除率、相對選擇性、無靜態蝕刻率方面皆發揮顯著優異之效果,此外本發明該研磨組成物的pH
值控制於7至12的範圍內,因此陰離子添加物不會形成對人體有害的氫氟酸,使用該研磨組成物進行矽鍺合金基材拋光時,可降低化學藥劑對人體及環境的傷害。
Claims (9)
- 一種研磨組成物,適用於矽鍺合金基材之研磨,包含:研磨顆粒;具有六價鉬或五價釩之化合物,用於直接對該矽鍺合金基材進行催化和氧化反應;以及載劑,其中該研磨顆粒的含量為0.01wt%至5wt%,該具有六價鉬或五價釩之化合物的含量為0.01wt%至1.0wt%;其中,該研磨組成物之pH值範圍為7至12;其中該研磨組成物還包含一陰離子添加物,其中該陰離子添加物的含量為0.01wt%至1.0wt%,且該陰離子添加物為選自氟化鉀,氟化鈉、氟化銨、三氟醋酸、三氟醋酸鉀、三氟醋酸鈉等所組成的族群中的至少一者。
- 如申請專利範圍第1項所述的研磨組成物,其中該研磨組成物還包含有一含鹵素氧化物之化合物或其鹽類,其中該鹵素氧化物之化合物或其鹽類的含量為0.05wt%至5wt%。
- 如申請專利範圍第1至2項中任一項所述的研磨組成物,其中該研磨顆粒為選自膠體二氧化矽或燻製二氧化矽。
- 如申請專利範圍第1至2項中任一項所述的研磨組成物,其中該具有六價鉬或五價釩之化合物為選自三氧化鉬、鉬酸、磷鉬酸、五氧化二釩、偏釩酸鈉與釩酸鈉等所組成的族群中的至少一者。
- 如申請專利範圍第2項所述的研磨組成物,其中該含鹵素氧化物之化合物或其鹽類為選自過碘酸鉀、碘酸鉀、過氯酸鉀、過氯酸鈉、氯酸鉀,氯酸鈉、次氯酸鈉等所組成的族群中的至少一者。
- 如申請專利範圍第1至2項中任一項所述的研磨組成物,其中該載劑包括水。
- 如申請專利範圍第1至2項中任一項所述的研磨組成物,用於矽鍺基材、矽基材與二氧化矽基材之化學機械拋光。
- 如申請專利範圍第7項所述的研磨組成物,其中在該矽鍺基材中鍺的含量為10%至80%。
- 如申請專利範圍第8項所述的研磨組成物,其中該矽鍺基材的靜態蝕刻速率為0埃/分鐘。
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EP3311415A4 (en) * | 2015-06-16 | 2019-01-16 | Intel Corporation | TRANSISTOR WITH A LUBLIC LAYER |
CN106244022A (zh) * | 2016-07-29 | 2016-12-21 | 曹蕊 | 用于氮化镓半导体晶片的研磨液及其制备方法 |
JP7507561B2 (ja) * | 2017-09-29 | 2024-06-28 | 株式会社フジミインコーポレーテッド | 研磨用組成物 |
JP7488672B2 (ja) * | 2020-03-19 | 2024-05-22 | 株式会社フジミインコーポレーテッド | 研磨方法および半導体基板の製造方法 |
CN112680229A (zh) * | 2021-01-29 | 2021-04-20 | 深圳市百通达科技有限公司 | 一种湿电子化学的硅基材料蚀刻液及其制备方法 |
CN115785824B (zh) * | 2022-12-21 | 2024-04-09 | 北京天科合达半导体股份有限公司 | 一种化学机械抛光液、其制备方法及应用 |
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CN100343189C (zh) * | 2000-04-28 | 2007-10-17 | 默克专利有限公司 | 用于无机表面的蚀刻糊 |
US6454821B1 (en) * | 2000-06-21 | 2002-09-24 | Praxair S. T. Technology, Inc. | Polishing composition and method |
US7186653B2 (en) * | 2003-07-30 | 2007-03-06 | Climax Engineered Materials, Llc | Polishing slurries and methods for chemical mechanical polishing |
WO2008069781A1 (en) * | 2006-12-04 | 2008-06-12 | Basf Se | Planarization composition for metal surfaces comprising an alumina hydrate abrasive |
US8541310B2 (en) | 2007-05-04 | 2013-09-24 | Cabot Microelectronics Corporation | CMP compositions containing a soluble peroxometalate complex and methods of use thereof |
KR20100037107A (ko) * | 2007-06-15 | 2010-04-08 | 바스프 에스이 | 구리 화학적 기계적 평탄화를 위한, 콜로이드성 입자, 고분자 전해질 및 이온성 첨가제를 사용하는 부동태화 필름 특성의 제어 |
CN101591508A (zh) * | 2008-05-30 | 2009-12-02 | 安集微电子(上海)有限公司 | 一种用于金属化学机械抛光的抛光浆料及其用途 |
CN101608098B (zh) * | 2008-06-20 | 2013-06-12 | 安集微电子(上海)有限公司 | 一种用于金属化学机械抛光的抛光浆料及其用途 |
JP5263400B2 (ja) * | 2009-08-19 | 2013-08-14 | 日立化成株式会社 | Cmp研磨液及び研磨方法 |
DE112010003900T5 (de) | 2009-10-02 | 2012-08-30 | Mitsubishi Gas Chemical Company, Inc. | Lösung zum Ätzen von Silizium und Ätz-Verfahren |
US20110291188A1 (en) | 2010-05-25 | 2011-12-01 | International Business Machines Corporation | Strained finfet |
US8889494B2 (en) | 2010-12-29 | 2014-11-18 | Globalfoundries Singapore Pte. Ltd. | Finfet |
SG11201403556WA (en) * | 2011-12-28 | 2014-07-30 | Advanced Tech Materials | Compositions and methods for selectively etching titanium nitride |
US9796881B2 (en) * | 2012-03-05 | 2017-10-24 | Fujimi Incorporated | Polishing composition and method using said polishing composition to manufacture compound semiconductor substrate |
JP6363116B2 (ja) * | 2013-03-04 | 2018-07-25 | インテグリス・インコーポレーテッド | 窒化チタンを選択的にエッチングするための組成物および方法 |
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US20160208141A1 (en) | 2016-07-21 |
TW201617431A (zh) | 2016-05-16 |
US9493678B2 (en) | 2016-11-15 |
CN105585965A (zh) | 2016-05-18 |
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