TW200911970A - A process for polishing patterned and unstructured surfaces of materials and an aqueous polishing agent to be used in the said process - Google Patents
A process for polishing patterned and unstructured surfaces of materials and an aqueous polishing agent to be used in the said process Download PDFInfo
- Publication number
- TW200911970A TW200911970A TW97121442A TW97121442A TW200911970A TW 200911970 A TW200911970 A TW 200911970A TW 97121442 A TW97121442 A TW 97121442A TW 97121442 A TW97121442 A TW 97121442A TW 200911970 A TW200911970 A TW 200911970A
- Authority
- TW
- Taiwan
- Prior art keywords
- polishing agent
- aqueous polishing
- metal
- group
- aqueous
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 176
- 238000000034 method Methods 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 114
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000007800 oxidant agent Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 75
- 229910052802 copper Inorganic materials 0.000 claims description 74
- 239000010949 copper Substances 0.000 claims description 74
- 230000001588 bifunctional effect Effects 0.000 claims description 30
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 claims description 29
- MSWZFWKMSRAUBD-QZABAPFNSA-N beta-D-glucosamine Chemical compound N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-QZABAPFNSA-N 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 19
- 229910052707 ruthenium Inorganic materials 0.000 claims description 19
- 229940126062 Compound A Drugs 0.000 claims description 18
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 18
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 15
- -1 poly(decyl) Polymers 0.000 claims description 15
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- 239000000126 substance Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000002161 passivation Methods 0.000 claims description 10
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- 229920000642 polymer Polymers 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002337 glycosamines Chemical class 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 6
- 229960002442 glucosamine Drugs 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 150000004697 chelate complex Chemical class 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 239000006174 pH buffer Substances 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- MSWZFWKMSRAUBD-GASJEMHNSA-N 2-amino-2-deoxy-D-galactopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@H](O)[C@@H]1O MSWZFWKMSRAUBD-GASJEMHNSA-N 0.000 claims 2
- 229910052684 Cerium Inorganic materials 0.000 claims 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 2
- 150000007529 inorganic bases Chemical class 0.000 claims 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000008119 colloidal silica Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 229920000131 polyvinylidene Polymers 0.000 claims 1
- 238000000518 rheometry Methods 0.000 claims 1
- 239000013522 chelant Substances 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 description 50
- 239000010410 layer Substances 0.000 description 42
- 235000012431 wafers Nutrition 0.000 description 18
- 230000004888 barrier function Effects 0.000 description 15
- 230000007547 defect Effects 0.000 description 14
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000000059 patterning Methods 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000003082 abrasive agent Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007517 polishing process Methods 0.000 description 4
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- 239000010931 gold Substances 0.000 description 3
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- 241000238631 Hexapoda Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Inorganic materials ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 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 2
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- GSDQYSSLIKJJOG-UHFFFAOYSA-N 4-chloro-2-(3-chloroanilino)benzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1NC1=CC=CC(Cl)=C1 GSDQYSSLIKJJOG-UHFFFAOYSA-N 0.000 description 1
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 238000009825 accumulation Methods 0.000 description 1
- FZHXIRIBWMQPQF-KCDKBNATSA-N aldehydo-D-galactosamine Chemical compound O=C[C@H](N)[C@@H](O)[C@@H](O)[C@H](O)CO FZHXIRIBWMQPQF-KCDKBNATSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- UAORAKLVHWMDLY-UHFFFAOYSA-N hydrazine hydrogen peroxide Chemical compound NN.OO UAORAKLVHWMDLY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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]
-
- 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
- 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
- C09K3/1463—Aqueous liquid suspensions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- 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
200911970 九、發明說明： 【發明所屬之技術領域】 本發月係針對—種拋光、尤其化學機械拋光（CM?)材料 圖案化及非結構化表面之新穎方法，其中使用至少—種 雙功能或多功能化合物。 此外，本發明係針對—種新穎水性拋光劑，尤其含有至 ' 少一種雙功能或多功能化合物之CMP試劑。 【先前技術】 ( ㈣電路⑽由結構化半導電、不導電及導電薄層組 成。此等圖案化層通常藉由(例如)以氣相沈積法塗覆一層 材料且藉由顯微飯刻方法使其圖案化來製備。藉助於、组合 各種半導電、不導電及導電層化材料，製造諸如電晶體、 電谷益、電阻器及導線之電子電路元件。 1C及其功此之品質尤其依賴於可塗覆及圖案化各層材料 之精確度。 d而隨著層數之增加，各層之平坦度顯著降低。此導 致1C之或夕個功能元件失效且因此使整個IC在達到一定 層數後失效。 各層之平坦度之降低係由新層堆累於已圖案化之層之頂 部引起。藉由圖案化產生可合計達每層G 6 _之高度差。 . &等咼度差層層累計且導致下-層不再能塗覆於平坦表面 上，且只能僅塗覆於不平坦表面上。最初結果為隨後塗覆 之層具有不規則厚度。在極端情況下，產生電子功能元件 之瑕疲、缺陷及電接點缺乏。此外，不平坦表面產生關於 131776.doc 200911970 圖案化之問題。為能夠报士 q200911970 IX. INSTRUCTIONS: [Technical field to which the invention pertains] This is a novel method for patterning and unstructured surfaces of polishing, especially chemical mechanical polishing (CM?) materials, using at least a dual function or Multifunctional compound. Furthermore, the present invention is directed to a novel aqueous polishing agent, especially a CMP agent containing at least one bifunctional or multifunctional compound. [Prior Art] (4) Circuit (10) consists of a structured semiconducting, non-conducting, and electrically conductive thin layer. These patterned layers are typically coated by a layer of material, for example, by vapor deposition and by microscopic engraving. It is prepared by patterning. By means of, combining various semi-conductive, non-conductive and conductive layered materials, electronic circuit components such as transistors, electric grids, resistors and wires are manufactured. 1C and its quality are particularly dependent on The accuracy of the material can be coated and patterned. d As the number of layers increases, the flatness of each layer is significantly reduced. This leads to the failure of 1C or a functional element and thus the entire IC after reaching a certain number of layers. The flatness of each layer is caused by the accumulation of a new layer on top of the patterned layer. The difference in height of each layer G 6 _ can be aggregated by patterning. Accumulating and causing the lower layer to no longer be applied to a flat surface and can only be applied to uneven surfaces. The initial result is that the subsequently applied layer has an irregular thickness. In extreme cases, electronic functional components are produced. Tired Lack of defects and electrical contacts. In addition, the uneven surface produces problems with the patterning of 131776.doc 200911970.
Am άλχ 成足夠小之圖案，極敏銳聚焦深 又在.，，員微I虫刻方法步驟中 n τ必不可少。然而’此等圖案僅可 於平坦表面上以銳度# 俞暗。 又成像。位置愈偏離平坦度，圖像變得 為解決此問題，進行所謂化學機械拋光(CMP)。CMP藉 :移除層之犬出特徵直至獲得平坦層來使圖案化表面總‘ 二旦化。因此，後續堆累可於展現無高度差之平坦表面之Am άλχ is a sufficiently small pattern, and it is extremely sharp and deep. In the case of micro-I insect method, n τ is essential. However, these patterns can only be sharp on the flat surface with sharpness. Also imaging. The more the position deviates from the flatness, the image becomes a solution to this problem, and so-called chemical mechanical polishing (CMP) is performed. CMP borrowing: removes the canine out feature of the layer until a flat layer is obtained to make the patterned surface total. Therefore, the subsequent stacking can be used to show a flat surface without height difference.
、P進4亍且圖案化及Ic元件功能性之精確度得以維持。 總體平坦化之典型實例為介電質CMP、磷化錄CMP及石夕 或聚矽CMP。 除用於克服微影困難之總體平坦化外，關於CMp存在兩 種其他重要應用。一種為製造微觀結構。此應用之典型實 例為銅CMP、鎢CMP或淺槽隔離（STI)CMp，尤其下文所述 之鑲肷方法（Damascene process)。另一種為缺陷校正或消 除，例如藍寶石CMP。 CMP方法步驟係借助於特定拋光機、拋光墊及在此項技 術中亦稱為拋光漿料或CMP漿料之拋光劑來進行。CMp. 料為組合物，其與拋光墊組合使得待拋光之材料得以移 除。 在拋光具有半導體層之晶圓的情況下’對於該方法步驟 之精確度要求及因此對於CMP漿料規定之要求尤為嚴格。 使用一系列參數來評估CMP漿料之效率且表徵其活性。 作為移除待拋光材料之速度的材料移除速率（MRR)、作為 待抛光材料之移除速率與其他所存在材料之移除速率的比 J31776.doc 200911970 2之選擇性、晶圓内之移除均一性（WIWNU;晶圓内不均 一性）及晶圓間之移除均一性（WTWNU ;晶圓間不岣—性 以及單位面積之缺陷數目屬於此等參數。 銅鑲嵌方法愈來愈多地用於製造IC(參看例如 利申請化A2，第2頁，第[0012]段）。為= 銅電路通道，需以此方法借助於CMP聚料以化學機械方式 移除銅層，該方法在此項技術中亦稱為"銅CMP方法"。^, P into 4 亍 and the accuracy of the patterning and Ic component functionality is maintained. Typical examples of overall planarization are dielectric CMP, phosphating CMP, and Shixi or poly CMP. In addition to the overall flattening used to overcome lithography difficulties, there are two other important applications for CMp. One is to make a microstructure. A typical example of this application is copper CMP, tungsten CMP or shallow trench isolation (STI) CMp, especially the Damascene process described below. The other is for defect correction or elimination, such as sapphire CMP. The CMP process steps are carried out by means of a specific polisher, polishing pad and a polishing agent also known in the art as a polishing slurry or CMP slurry. CMp. is a composition which, in combination with a polishing pad, allows the material to be polished to be removed. In the case of polishing wafers with semiconductor layers, the accuracy requirements for this method step and therefore the requirements for CMP slurry specifications are particularly critical. A series of parameters were used to evaluate the efficiency of the CMP slurry and characterize its activity. The material removal rate (MRR) as the speed at which the material to be polished is removed, the ratio of the removal rate of the material to be polished to the removal rate of other materials present, J31776.doc 200911970 2, the in-wafer shift In addition to uniformity (WIWNU; in-wafer heterogeneity) and inter-wafer removal uniformity (WTWNU; inter-wafer non-slipness and the number of defects per unit area belong to these parameters. More and more copper mosaic methods Used to manufacture ICs (see, for example, Application A2, page 2, paragraph [0012]). = = copper circuit channel, in this way chemically mechanically removes the copper layer by means of CMP material. Also known in the art as "copper CMP method".^
C 所完成鋼電路通道嵌入介電質中。通常，將障壁層定 銅與該介電質之間。 ； 關於銅CMP方法已知兩步驟方法。此意謂在第—步驟中 用保證高銅移除速率之CMP漿料拋光銅層。在第二步驟 中所使用第二CMP聚料以產生具有經拋光露出且平滑二介 電質及嵌入之銅電路通道的最後平坦表面。 5亥第一步驟通常分為兩個階段。 在第-階段期間，顯著減小或消除銅結構之階梯高度。 平坦銅表面為所需結果。 在第一 h ^又期間，移除殘餘之銅臈。 、因此’第—階段之關鍵目的為減小階梯高度。相對移除 =率選擇性並不重要。當在第二階段期間將達到障壁及可 能之介電材料時，移除速率選擇性較重要。第二階段之關 鍵目的在於防止階梯高舟 又再生成、使表面缺陷減至最少及 清除所有銅殘餘物。 對於第-拋光步驟而言’使用具有高度選擇性之咖漿 料。此意謂銅之移除速率儘可能高且下層障壁層之移除速 13I776,doc 10· 200911970 率儘可能低。一旦自銅下方挖出障壁層，則拋光過程自動 停止。然而，因為自障壁層完全移除銅殘餘物需花費一些 時間，其在此項技術中亦稱為”過拋光（over p〇lishing)”， 所以於銅電路通道嵌入介電質之位置處不斷地移除電路通 道之銅。此效應在此項技術中亦稱為”表面凹陷"。視第一 拋光步驟中所產生之表面之設計及品質而定，在第二拋光 步驟中使用對於待拋光材料（亦即銅、障壁層及介電質）具 選擇性或不具選擇性之CMP浆料。 在均一移除銅之情況下，僅在障壁層後留下極少銅殘餘 物可在弟一拋光步驟中達成，在第二拋光步驟中使用對於 障壁層具有極高選擇性之CMP漿料以獲得均一拋光表面。 在於第一拋光步驟中產生障壁層上仍然含有銅之表面的 清况下，推薦使用對於障壁層不具選擇性之CMp漿料。在 使用非選擇性CMPt料之情況下，亦即在對於銅、障壁層 及介電質之移除速率大致相等之情況下，藉由拋光方法使 整個晶圓表面均一平坦化。然而，須犧牲介電層之—部 分，由於沈積較厚介電層及銅層之必要性，因此其為不利 的。非選擇性CMP聚料有必要對於所有三種待抛光材料具 有基本上相同之平坦化效率。此外，所產生之銅電路通道 須具有最小厚纟’此意謂必須注意不能自介電層及鋼電路 通道移除過多材料。gut，必須在拋光過程期間謹慎 測移除。 Mi 在第二拋光步驟中使用選擇性0^]?漿料之情況下，障壁 層之移除速率高於銅之移除速率。在該種狀況下，鋼電路 131776.doc 200911970 通道之表面凹陷藉由選擇性移除障壁層來減輕。因此，介 電質之損失（亦即侵蝕）及與其相關之銅電路通道之層厚度 的減小少的多。 自所有此等描述，可推斷出CMP漿料、尤其銅CMP漿料 之材料組成對於先前所述之CMP方法非常重要。 3有固體細粉狀研磨劑（例如膠態二氧化矽）、氧化劑（例 、氣化風）此夠形成水溶性銅螯合錯合物之螯合劑（諸 如甘胺酸）及腐蝕抑制劑、鈍化劑或臈構成劑（例如苯并三 唑）之銅CMP漿料自國際專利申請案w〇 2004/063301 A1已 知。四種組份（研磨劑、氧化劑、鈍化劑及螯合劑）間之平 衡作用提供減小階梯高度之所需機制。 然而，存在與銅CMP漿料之該典型設計相關之許多缺 點，包括螯合劑之腐蝕作用、由典型鈍化劑引入之缺陷及 諸如由由鈍化劑導致之較大研磨劑顆粒引起之刮痕及坑洞 的表面缺陷。亦已展示使用不含研磨劑之CMP聚料可減少 諸如刮痕之表面缺陷，但此由於系統中補償缺乏研磨劑所 品之強化學組份而導致諸如腐蝕之併發症。 美國專利申請案US 2002/0183498 A1揭示含有諸如聚葡 萄胺糖之聚葡糖胺及諸如過氧化氫之氧化劑之水性漿料。 由於添加銅離子，此等水性漿料之聚葡萄胺糖濃度可顯著 增加。此等水性漿料之pH值較佳在4至6之範圍内且可借助 於有機酸及無機酸進行調整。此等先前技術水性漿料係用 作殺真菌劑。在無論何種專利申請案中均未提及其可用作 拋光劑或用於拋光劑中。 131776.doc -12- 200911970 【發明内容】 本發明之目的 本發明之目的在於提供一種用於拋光、尤其用於材料之 圖案化及非結構化表面、較佳材料之圖案化表面、更佳金 屬及金屬-介電質圖案、尤其含銅圖案之CMP的新穎水性 拋光劑’該等新穎拋光劑並不展現先前技術之缺點。 詳言之，新穎水性拋光劑應具有較少複合材料組成以便 其可適合於各個別情況之要求而比先前技術之銅CMp漿料 好的多。新穎水性拋光劑應具有優良拋光效率而不會在銅 鑲欲方法期間引起表面凹陷。新穎水性拋光劑應不展現不 當腐蝕作用且不應招致待拋光材料中之缺陷、到痕及坑 洞0 此外，本發明之目的在於提供一種新穎拋光方法，較佳 材料之圖案化及非結構化、較佳圖案化表面、最佳金屬及 金屬-介電質結構且尤其含銅結構之新穎CMP方法，該新 穎拋光方法不再展現先前技術之缺點且不招致待拋光材料 中之表面凹陷且不導致不當腐蝕及待拋光材料中之缺陷、 刮痕及坑洞。 本發明之概述 因此，已發現拋光材料之圖案化及非結構化表面之新穎 方法，其中使用水性拋光劑，該水性拋光劑包含： (A)至少一種雙功能或多功能化合物 (a〇能夠於金屬Μ或該金屬Μ之合金之表面的頂部由其水 性溶液及/或分散液形成鈍化膜’該金屬Μ對於以下半反應 131776.doc 13 200911970 具有大於-o.l v之標準還原電位E〇 M^>Mn++ne_，其中n=l至4之整數且e-=電子； 且同時， (a2)此夠與水性溶液及/或分散液中之該金屬μ及/或其離 子形成螯合錯合物；及 (Β)至少一種氧化劑。 在下文中’該新穎拋光方法稱為"本發明之拋光方法”。 另外’發現新穎水性拋光劑，其含有： (Α)至少一種雙功能或多功能化合物 (al)能夠於金屬μ或該金屬Μ之合金之表面的頂部由其水 I"生/谷液及/或分散液形成純化膜，該金屬Μ對於以下半反應 具有大於-0.1 V之標準還原電位Ε0 Μ㈠Mn++n e_，其中η=ι至4之整數且e-=電子； 且同時， (a2)把夠與水性溶液及/或分散液中之該金屬μ及/或其離 子形成螯合錯合物； (Β)至少一種氧化劑；及 (C)至少一種固體細粉狀研磨劑。 在下文中，該新穎水性拋光劑稱為”本發明之拋光劑,，。 本發明之優點 鑒於以上所論述之先前技術，令人驚訝地且熟習技術者 未預期到，作為本發明之基礎之目的可藉由本發明方法及 本發明之拋光劑來解決。 詳言之，令人驚訝的是雙功能或多功能化合物Α之新穎 131776.doc • 14- 200911970 使用允許製造水性拋光劑、較佳本發明之拋光劑，其結合 本發明之拋光方法極好地適合於材料之圖案化及非結構化 表面、較佳材料之圖案化表面、最佳金屬及金屬-介電質 圖案、尤其含銅圖案之拋光、較佳CMP。 更具體而言’所關注之用於CMP之抛光劑、尤其本發明 之用於CMP之抛光劑完全適合於含有金屬μ或該金屬Μ之 合金或由金屬Μ或該金屬Μ之合金組成之金屬及金屬-介電 質結構的CMP ’該金屬Μ對於以下半反應具有大於_〇. 1 ν 之標準還原電位Ε0 MMMn++ne’，其中η=ι至4之整數且e_=電子； 但尤其為銅。特定言之，用於本發明之拋光方法中之拋 光劑極好地適合於用於1(：之銅鑲嵌製造方法中之CmP。 此外’令人驚訝的是雙功能或多功能化合物A之新穎使 用允許使用於本發明之拋光方法中之水性拋光劑、尤其本 發明之拋光劑的材料組成簡單、高度特殊及可極好地再現 地適應及適合於個別情況之要求’尤其在材料移除速率 (MRR)及選擇性方面 。最值得注意，實現使水性拋光劑之C completed the steel circuit channel embedded in the dielectric. Typically, the barrier layer is between the copper and the dielectric. A two-step process is known for copper CMP methods. This means polishing the copper layer with a CMP slurry that ensures a high copper removal rate in the first step. The second CMP polymer is used in the second step to produce a final flat surface having polished exposed and smooth dielectric and embedded copper circuit channels. The first step of 5 Hai is usually divided into two stages. During the first phase, the step height of the copper structure is significantly reduced or eliminated. A flat copper surface is the desired result. During the first h ^ period, the residual copper plaque is removed. Therefore, the key purpose of the 'stage' is to reduce the step height. Relative removal = rate selectivity is not important. The removal rate selectivity is important when the barrier and possible dielectric materials will be reached during the second phase. The key to the second phase is to prevent the ladder from re-generating, minimizing surface defects and removing all copper residues. For the first polishing step, a highly selective coffee slurry is used. This means that the removal rate of copper is as high as possible and the removal rate of the lower barrier layer is 13I776, and the rate of doc 10·200911970 is as low as possible. Once the barrier layer is dug out from under the copper, the polishing process stops automatically. However, since it takes some time to completely remove the copper residue from the barrier layer, which is also referred to as "over p〇lishing" in the art, it is constantly placed at the position where the copper circuit channel is embedded in the dielectric. Ground removes copper from the circuit path. This effect is also referred to in the art as "surface depression". Depending on the design and quality of the surface produced in the first polishing step, the material to be polished (ie, copper, barrier) is used in the second polishing step. Layer and dielectric) CMP slurry with selective or non-selective. In the case of uniform removal of copper, leaving only a small amount of copper residue behind the barrier layer can be achieved in the polishing step, in the second A CMP slurry having a very high selectivity to the barrier layer is used in the polishing step to obtain a uniform polished surface. In the case where the surface of the barrier layer still contains a copper surface in the first polishing step, it is recommended that the barrier layer is not selective. CMp slurry. In the case of using a non-selective CMPt material, that is, the removal rate of copper, barrier layer and dielectric is substantially equal, the entire wafer surface is uniformly planarized by a polishing method. However, it is necessary to sacrifice the portion of the dielectric layer, which is disadvantageous due to the necessity of depositing a thick dielectric layer and a copper layer. It is necessary for the non-selective CMP polymer to be used for all three materials to be polished. It has substantially the same planarization efficiency. In addition, the resulting copper circuit path must have a minimum thickness 纟 'This means that it must be noted that too much material cannot be removed from the dielectric layer and the steel circuit path. Gut must be cautious during the polishing process The removal is performed. In the case where the selective 0^]? slurry is used in the second polishing step, the removal rate of the barrier layer is higher than the removal rate of copper. Under this condition, the steel circuit 131776.doc 200911970 The surface depression of the channel is mitigated by the selective removal of the barrier layer. Therefore, the dielectric loss (ie, erosion) and the thickness of the layer of the copper circuit channel associated therewith are much less reduced. It can be inferred that the material composition of the CMP slurry, especially the copper CMP slurry, is very important for the CMP method described previously. 3 There are solid fine powder abrasives (such as colloidal cerium oxide), oxidants (for example, gasification wind) A copper CMP slurry sufficient to form a water-soluble copper chelate complex chelating agent (such as glycine) and a corrosion inhibitor, passivating agent or bismuth constituting agent (such as benzotriazole) from the international patent application. 2004/063 301 A1 is known. The balance between the four components (abrasives, oxidizers, passivators, and chelating agents) provides the mechanism needed to reduce the step height. However, there are many related to this typical design of copper CMP slurries. Disadvantages include corrosive effects of chelating agents, defects introduced by typical passivating agents, and surface defects such as scratches and potholes caused by larger abrasive particles caused by passivating agents. CMP without abrasives has also been shown. Aggregates can reduce surface defects such as scratches, but this can result in complications such as corrosion due to the lack of a strong chemical component of the abrasive in the system. US Patent Application No. US 2002/0183498 A1 discloses the inclusion of, for example, polyglucamine Aqueous slurries of sugar polyglucosamine and an oxidizing agent such as hydrogen peroxide. The concentration of polyglucosamine in such aqueous slurries can be significantly increased due to the addition of copper ions. The pH of these aqueous slurries is preferably in the range of 4 to 6 and can be adjusted by means of organic acids and inorganic acids. These prior art aqueous slurries are used as fungicides. It is not mentioned in any patent application as a polishing agent or in a polishing agent. 131776.doc -12- 200911970 SUMMARY OF THE INVENTION Objects of the Invention It is an object of the present invention to provide a patterned and unstructured surface for use in polishing, particularly for materials And novel water-based polishes for metal-dielectric patterns, especially CMP containing copper patterns, which do not exhibit the disadvantages of the prior art. In particular, the novel aqueous polishes should have a lesser composite composition so that they can be tailored to the individual requirements and are much better than prior art copper CMp slurries. The novel aqueous polish should have excellent polishing efficiency without causing surface depression during the copper inlay process. The novel water-based polishing agent should not exhibit improper corrosion and should not cause defects, marks and pits in the material to be polished. Furthermore, the object of the present invention is to provide a novel polishing method, which is patterned and unstructured. Novel CMP method, preferably patterned surface, optimal metal and metal-dielectric structure and especially copper structure, the novel polishing method no longer exhibits the disadvantages of the prior art and does not cause surface depressions in the material to be polished and does not Causes improper corrosion and defects, scratches and potholes in the material to be polished. SUMMARY OF THE INVENTION Accordingly, novel methods of patterning and unstructured surfaces of polishing materials have been discovered in which an aqueous polishing agent is used, the aqueous polishing agent comprising: (A) at least one bifunctional or multifunctional compound (a) The top of the surface of the metal tantalum or the alloy of the tantalum is formed into a passivation film from its aqueous solution and/or dispersion. The metal tantalum has a standard reduction potential E〇M^ greater than -ol v for the following half reaction 131776.doc 13 200911970 >Mn++ne_, where n = an integer from 1 to 4 and e- = electron; and at the same time, (a2) is sufficient to chelate the metal μ and/or its ions in the aqueous solution and/or dispersion The complex compound; and (Β) at least one oxidizing agent. Hereinafter, the novel polishing method is referred to as "the polishing method of the present invention". In addition, 'a novel aqueous polishing agent is found, which contains: (Α) at least one bifunctional or multi-functional The functional compound (al) is capable of forming a purified film from the water I" raw/column liquid and/or dispersion at the top of the surface of the metal μ or the alloy of the metal tantalum, the metal tantalum having a greater than -0.1 V for the following half reaction Standard reduction potential Ε0 Μ (a) Mn++n e_, wherein η = ι to an integer of 4 and e- = electron; and at the same time, (a2) is sufficiently chelating with the metal μ and/or its ions in the aqueous solution and/or dispersion (Β) at least one oxidizing agent; and (C) at least one solid fine powder abrasive. Hereinafter, the novel aqueous polishing agent is referred to as "the polishing agent of the present invention," the advantages of the present invention are in view of the above discussion The prior art, surprisingly and familiar to the skilled person, is not intended to be solved by the method of the present invention and the polishing agent of the present invention. In particular, it is surprisingly bi-functional or multi-functional. The novelty of the functional compound 131 776 776 131 131 131 131 131 131 131 131 131 776 776 776 776 776 776 776 776 776 776 776 776 776 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 a patterned surface of a good material, an optimum metal and a metal-dielectric pattern, especially a copper-containing pattern, preferably CMP. More specifically, 'the polishing agent of interest for CMP, especially for the present invention CMP polishing agent is completely CMP suitable for alloys containing metal μ or the metal ruthenium or metal and metal-dielectric structures composed of metal ruthenium or an alloy of the ruthenium metal Μ 'The metal ruthenium has a standard greater than _〇. 1 ν for the following half reaction Reduction potential Ε0 MMMn++ne', wherein η = ι to an integer of 4 and e_ = electron; but especially copper. In particular, the polishing agent used in the polishing method of the present invention is excellently suitable for use in 1 (CmP in the copper inlay manufacturing method. Further, 'surprisingly, the novel use of the bifunctional or multifunctional compound A allows the use of the aqueous polishing agent used in the polishing method of the present invention, especially the polishing agent of the present invention. The composition is simple, highly specific and can be reproducibly adapted and adapted to the individual case requirements, especially in terms of material removal rate (MRR) and selectivity. Most noteworthy, to achieve a water-based polish
不含腐餘、刮痕、 ~〜观尤劑展現優艮拋光效率。詳言 料移除速率（MRR)及極高選擇性且產生 坑洞或其他缺陷之拋光表面。然而最值 131776.doc 15 200911970 得注意，其在銅鑲嵌方 中不引起表面凹陷或僅引起可忽 視之小表面凹陷。 uIt does not contain corrosion, scratches, and ~~ Detailed material removal rate (MRR) and polished surfaces that are extremely selective and create pits or other defects. However, the maximum value is 131776.doc 15 200911970 It is noted that it does not cause surface depression or only negligible small surface depressions in the copper mosaic. u
最後但並非最不重I 重要，雙功能化合物A之新穎使用允許 用不含有固體、精細八 、'、刀放研磨劑之水性拋光劑進行本發明 之拋光方法以便不再出現常常與其相關之缺點，諸如刮痕 或坑洞。“，所關注之水性拋光劑形成與含有研磨劑之 水性拋光劑相同劣继& m x i ^ 乎相同之優良抛光效率而不引起腐 独0 總而言之’本發明之拋光方法及本發明之拋光劑展現一 方面用於犬出圖案或結構之特別高的材料移除速率⑽ 與另方面用於低陷或内凹圖案或結構之特別強的保護作 用之間的優良平衡。 因此，由於雙功能或多功能化合物A於本發明之拋光方 法及本發明之拋光劑中之新穎使用，可製造不具有 WIWNU或僅具有可忽視的小wiWNU及不具有WTWNU或 僅具有可忽視的小WTWNU之具有1C之晶圓。因此，可達 成格外高之製造效率。 【實施方式】 在其最廣泛態樣中，本發明係針至少一種如下文所定義 之雙功能或多功能化合物A於用於本發明之拋光方法中之 水性拋光劑及於本發明之拋光劑中的新穎用途。 因此’用於本發明之拋光方法中之水性拋光劑以及本發 明之拋光劑包含至少一種、較佳一種雙功能或多功能、較 佳雙功能化合物A。 131776.doc -16- 200911970 基本上，術語”雙功能或多功能，，意謂該化合物A可完成 水性拋光劑之至少兩種、尤其兩種功能，該兩種功能在化 學及物理化學方面彼此不同。 在其第一功能a 1中，該螫喊处# 又力月b或多功能化合物a能夠於 金屬Μ或該金屬Μ之合金之表面的頂部由其水性溶液及/或 分散液形成鈍化膜，該金相對於以下半反應具有大於- V，較佳大於〇 V，最佳大於〇ι ν且尤其大於〇2ν之 標準還原電位E0 Μ㈠Mn++ne_，其中^丨至斗之整數且e_=電子。 該大於-CM之標準還原電㈣。之實例列於CRcHandb〇〇k〇f ChemiStry — Physics，第 79版，1998_1999, CRC 卜⑶ LLC, Electrochemical Series，8-21 至 8-31 中。 在本發明之上下文中，術語”純化膜表示基本上或完全 由至少-種、較佳一種雙功能或多功能化合物A組成之單 層或多層膜。該鈍化膜黏著於金相或其合金之表面以便 保護該表面在本發明之拋光方法之條件下免受有害化學及 機械作用’尤其腐敍及消融之影響。在其第二功㈣中， 雙功能或多功能化合物A能夠與水性溶液及/或分散液中之 金屬Μ及/或其離子形成螯合錯合物。關於術語"餐合錯合 物'，請參考 RoemPP Online 2006, "chelates"。 已發現雙功能或多功能化合物八之下列令人驚譯的有利 作用。 員技術中已知鈍化膜通常由兩個層組成。第一層為橋 化或非氧化金屬表面及疏水性堆疊膜之黏著層。該疏 I31776.doc -17· 200911970 水性，疊膜為鈍化作用之關鍵。然而，其亦為習知純化劑 吞夕缺’”占之來源’该等缺點諸如有機殘餘物及促進形成 引=缺陷之顆粒。如此項技術中所已知，錯合劑具有雙 ^功能。第-功能在於藉由使黏著層膨脹而軟化疏水性堆 豐。另一功能在於快速溶解由疏水性鈍化劑包圍之氧化金 屬表面之金屬氧化物或氫氧化物。 然而，因此令人驚訝地，欲根據本發明使用之雙功能或 多功能化合物A、較佳親水性雙功能或多功能化合物A並 :需要任何其他錯合劑來使氧化金屬表面之金屬氧化物或 氫氧化物免於形成引^大缺陷之顆粒。另彳，雙功能或多 功能化合物A之親水性質較佳亦令人驚訝且有利地簡化鈍 化膜之結構。存在於習知⑽漿料之純化層中之黏著層及 疏水!·生堆$被由以氫鍵結合在一起之錯合物層及堆疊組成 之簡單臈置換。 較佳地，金屬Μ係選自由Ag、Au、Bi、Cu、Ge、^、 Os Pd、Pt、Re、Rh、ru、丁丨及w組成之群最佳選自Last but not least, I. The novel use of the bifunctional compound A allows the polishing process of the present invention to be carried out with an aqueous polishing agent that does not contain solids, fine eight, and knife-grinding abrasives so that the disadvantages often associated with it are no longer present. , such as scratches or potholes. "The aqueous polishing agent of interest forms the same excellent polishing efficiency as the aqueous polishing agent containing the abrasive, and does not cause corrosion. In general, the polishing method of the present invention and the polishing agent of the present invention are exhibited. On the one hand, a particularly high material removal rate (10) for a canine pattern or structure and an excellent balance between the other aspects of a particularly strong protection for a depressed or concave pattern or structure. The novel use of the functional compound A in the polishing method of the present invention and the polishing agent of the present invention can produce a crystal having 1C without WIWNU or having only negligible small wiWNU and having no WTWNU or only negligible small WTWNU Circle. Therefore, an extremely high manufacturing efficiency can be achieved. [Embodiment] In its broadest aspect, the present invention is characterized in that at least one bifunctional or multifunctional compound A as defined below is used in the polishing method of the present invention. A water-based polishing agent and a novel use thereof in the polishing agent of the present invention. Therefore, the aqueous polishing agent used in the polishing method of the present invention and the present invention The polishing agent comprises at least one, preferably one bifunctional or multifunctional, preferably bifunctional compound A. 131776.doc -16- 200911970 Basically, the term "bifunctional or multifunctional" means that the compound A can be subjected to aqueous polishing. At least two, and in particular two, functions of the agents which differ chemically and physicochemically from each other. In its first function a 1 , the screaming point #又月月 b or the multifunctional compound a can form a passivation film from the aqueous solution and/or dispersion at the top of the surface of the metal ruthenium or the alloy of the metal ruthenium, The gold has a standard reduction potential E0 Μ(1) Mn++ne_, which is greater than -V, preferably greater than 〇V, and preferably greater than 〇ι, and is particularly greater than 〇2ν, where ^^ is an integer to the bucket and e_=electron . This is greater than -CM standard reduction power (four). Examples are listed in CRcHandb〇〇k〇f ChemiStry — Physics, 79th edition, 1998_1999, CRC (3) LLC, Electrochemical Series, 8-21 to 8-31. In the context of the present invention, the term "purified film" denotes a single or multilayer film consisting essentially or entirely of at least one, preferably one, bifunctional or multifunctional compound A. The passivation film is adhered to a metallographic or alloy thereof. Surface to protect the surface from harmful chemical and mechanical effects, particularly rot and ablation, under the conditions of the polishing method of the present invention. In its second work (4), the bifunctional or multifunctional compound A can be combined with an aqueous solution and / or metal ruthenium and / or its ions in the dispersion to form a chelate complex. For the term "meal complex", please refer to RoemPP Online 2006, "chelates". Bifunctional or multifunctional compounds have been found. The following surprisingly beneficial effects of the eight are known. The passivation film is generally composed of two layers. The first layer is a bridged or non-oxidized metal surface and an adhesive layer of a hydrophobic stacked film. -17· 200911970 Water-based, laminated film is the key to passivation. However, it is also a well-known purification agent, which is the source of such defects, such as organic residues and promote the formation of defects. Particles. As is known in the art, the cross-linking agent has a dual ^ function. The first function is to soften the hydrophobic buildup by expanding the adhesive layer. Another function is to rapidly dissolve the metal oxide or hydroxide of the oxidized metal surface surrounded by the hydrophobic passivating agent. However, it is therefore surprisingly desirable to use the bifunctional or multifunctional compound A, preferably the hydrophilic bifunctional or multifunctional compound A according to the invention and: any other complexing agent is required to oxidize the metal oxide of the metal surface or The hydroxide is free from the formation of particles that cause large defects. Alternatively, the hydrophilic nature of the bifunctional or multifunctional compound A is preferred and surprisingly and advantageously simplifies the structure of the passivating film. The adhesive layer and the hydrophobic layer present in the purification layer of the conventional (10) slurry are replaced by a simple ruthenium consisting of a complex layer and a stack of hydrogen bonds. Preferably, the metal lanthanide is selected from the group consisting of Ag, Au, Bi, Cu, Ge, ^, Os Pd, Pt, Re, Rh, ru, butyl and w.
Ag、Au、Cu、Ir、〇s、pd、pt、Re、Rh、以及 ％ 金屬 M尤其為銅。 因此，在欲根據本發明使用之雙功能化合物A之水性溶 液及/或分散液與金屬Μ或其合金彼此直接接觸之情況下， 雙功此化合物Α根據其第一功能ai於金屬Μ或其合金之表 面上形成鈍化膜且同時根據其第二功能32與存在於水性溶 液及/或分散液中之金屬Μ及/或其離子形成螯合錯合物。 根據本發明，所有雙功能或多功能化合物Α可用於本發 13l776.doc -18- 200911970 明之拋光方法之水性拋光劑_或本發明之拋光劑中，只要 其於水性溶液或分散液中穩定且能夠完成功能a丨及a2即 可。術語"穩定’'意謂所關注之雙功能或多功能化合物A不 會不可逆地化學轉化’尤其不會由存在於水性拋光劑中之 水或其他組份分解。 較佳地，雙功能或多功能、尤其雙功能化合物A係選自 由胺基糖及其寡聚物及聚合物組成之群，更佳選自胺基糖 及聚葡糖胺’最佳選自D-葡糖胺、D_半乳糖胺及聚葡糖 胺，且尤其選自D-葡糖胺及聚葡萄胺糖。 本發明之拋光方法之水性拋光劑及本發明之拋光劑可含 有廣泛變化量之雙功能或多功能化合物A。因此，所關注 之量可極好地適應及適合於個別情況之要求。較佳地，拋 光劑含有0.1重量％至5重量❶/。、最佳0.丨重量％至3重量％且 尤其0.25重量％至2重量％之雙功能化合物a，各值以所關 注之完整拋光劑之重量計。 本發明之拋光方法之水性拋光劑視情況含有且本發明之 拋光劑必須含有至少一種、較佳一種氧化劑B。在本發明 之拋光方法之水性拋光劑用於CMP的情況下，其亦包含氧 化劑B。 氧化劑B可選自此項技術中通常用於CMp之氧化劑之 群。合適氧化劑B之實例自國際專利申請案w〇 2〇(Μ/〇633〇1第n頁第[〇〇28]段或自歐洲專利申請案工 鳩415八2第4頁第[〇〇5〇]段已知’該等申請案之揭/示内容 以引用的方式包括在本文中。詳言之’使用過氧化氣作為 131776.doc 19 200911970 氧化劑B。 本發明之拋光方法之水性拋光劑及本發明之拋光劑可含 有廣泛變化量之氧化劑B。因此’所關注之量可極好地適 應及適合於個別情況之要求。較佳地，拋光劑含有〇. 1重 量％至8重量％且尤其0.25重量％至5重量❹/〇之氧化劑B，各 值以所關注之完整拋光劑之重量計。 本發明之拋光方法之水性拋光劑視情況含有且本發明之 拋光劑必須含有至少一種、尤其一種固體細粉狀研磨劑 C。 本發明之拋光方法之一特定優點在於其亦可在許多情況 下用不含有固體細粉狀研磨劑c之水性抛光劑進行。因 此，有時與該等研磨劑相關之諸如拋光材料中之刮痕或坑 >同的缺點可自一開始就避免而不會危及拋光效率。本發明 之拋光方法之另一特殊優點在於不需要以高活性、尤其強 烈腐蝕性化合物來補償。 然而，由於其固體細粉狀研磨劑c之含量，本發明之拋 光劑一方面展現用於突出圖案或結構之格外高的MRR，而 另一方面不危及對於低陷圖案或結構之特別強的保護作 用。 較佳地，固體細粉狀研磨劑C具有i nm至300 nm、最佳5 nm至200 nm且尤其1〇 11〇1至1〇〇 nm之粒度。粒度分布視個 別情況之要求而定且可為單峰、雙峰或多峰，尤其為單 峰，且其可具有寬或窄分布範圍’尤其具有窄分布範圍早 幸父佳地，平均粒徑心❹在亏11111至5〇 nm之範圍内。粒度分布 131776.doc -20· 200911970 可藉由雷射繞射來測定。 顆粒c可具有不同形狀。舉例而言，其可具有立方體、 具有削邊之立方體、八面體、二十面體、不規則球粒或有 或無突起或缺口之球體之形狀。其尤其為無突起及 球形。 、 此外’顆粒C可為均質材料或非均質材料，諸如複合材 料。其可具有空心或其可為緻密的。其亦可經表面改質。 其尤其為均質且緻密的。Ag, Au, Cu, Ir, 〇s, pd, pt, Re, Rh, and % Metal M is especially copper. Therefore, in the case where the aqueous solution and/or dispersion of the bifunctional compound A to be used according to the present invention is in direct contact with the metal ruthenium or an alloy thereof, the compound Α is based on its first function ai in the metal ruthenium or A passivation film is formed on the surface of the alloy and at the same time forms a chelate complex according to its second function 32 with the metal ruthenium and/or its ions present in the aqueous solution and/or dispersion. According to the present invention, all of the bifunctional or multifunctional compound oxime can be used in the aqueous polishing agent of the polishing method of the present invention, or the polishing agent of the present invention, as long as it is stable in an aqueous solution or dispersion and The functions a丨 and a2 can be completed. The term "stable" means that the bifunctional or multifunctional compound A of interest does not irreversibly chemically convert' especially from the decomposition of water or other components present in the aqueous polishing agent. Preferably, the bifunctional or multifunctional, especially bifunctional compound A is selected from the group consisting of amino sugars and oligomers thereof and polymers, more preferably selected from the group consisting of amino sugars and polyglucosamines. D-glucosamine, D_galactosamine and polyglucosamine, and in particular from D-glucosamine and polyglucamine. The aqueous polishing agent of the polishing method of the present invention and the polishing agent of the present invention may contain a widely varying amount of the bifunctional or multifunctional compound A. Therefore, the amount of interest can be well adapted and adapted to the requirements of individual situations. Preferably, the polishing agent contains from 0.1% by weight to 5% by weight. Preferably, from 0% by weight to 3% by weight and especially from 0.25 % by weight to 2% by weight of the bifunctional compound a, each value being based on the weight of the complete polishing agent concerned. The aqueous polishing agent of the polishing method of the present invention is optionally contained and the polishing agent of the present invention must contain at least one, preferably one, oxidizing agent B. In the case where the aqueous polishing agent of the polishing method of the present invention is used for CMP, it also contains the oxidizing agent B. The oxidizing agent B may be selected from the group of oxidizing agents commonly used in the art for CMp. Examples of suitable oxidizing agents B are from the international patent application w〇2〇(Μ/〇633〇1第n页第[〇〇28] or from the European Patent Application 鸠 八 2 2 2 第 第 〇〇 〇〇 〇〇 〇〇段] Sections are known as 'the disclosure/description of these applications are incorporated herein by reference. 'Detailed use of peroxidation gas as 131776.doc 19 200911970 oxidizer B. Waterborne polishing agent for polishing method of the present invention And the polishing agent of the present invention may contain a wide variety of oxidizing agents B. Therefore, the amount of interest can be excellently adapted and adapted to the requirements of individual cases. Preferably, the polishing agent contains 〇. 1% by weight to 8% by weight. And especially from 0.25 wt% to 5 wt% 〇/〇 of the oxidizing agent B, each value being based on the weight of the complete polishing agent of interest. The aqueous polishing agent of the polishing method of the present invention is optionally contained and the polishing agent of the present invention must contain at least one In particular, a solid fine powder abrasive C. One of the particular advantages of the polishing method of the present invention is that it can also be carried out in many cases with an aqueous polishing agent which does not contain the solid fine powder abrasive c. Therefore, sometimes with Abrasive related The same disadvantages as scratches or pits in polishing materials can be avoided from the outset without compromising polishing efficiency. Another particular advantage of the polishing method of the present invention is that it does not require high activity, especially highly corrosive compounds. Compensating. However, due to the content of its solid fine powdered abrasive c, the polishing agent of the present invention exhibits an exceptionally high MRR for protruding patterns or structures on the one hand, and does not endanger the special pattern or structure for low depressions on the other hand. Strongly protective effect. Preferably, the solid fine powder abrasive C has a particle size of i nm to 300 nm, preferably 5 nm to 200 nm and especially 1 〇 11 〇 1 to 1 〇〇 nm. Depending on the requirements and may be unimodal, bimodal or multimodal, especially a single peak, and it may have a wide or narrow distribution range 'especially with a narrow distribution range, good fortune, the average particle diameter is at a loss 11111 Within the range of 5 〇 nm, the particle size distribution 131776.doc -20· 200911970 can be determined by laser diffraction. The particles c can have different shapes. For example, it can have a cube, a cube with a chamfered edge, and eight Face, two The shape of the facet, the irregular spherule or the sphere with or without protrusions or notches. It is especially non-protrusive and spherical. Furthermore, the 'particle C can be a homogeneous material or a heterogeneous material, such as a composite material. It can have a hollow or It can be dense. It can also be surface modified. It is especially homogeneous and dense.
較佳地，固體精細分散研磨劑C係選自由有機及無機材 料組成之群，該等材料在CMP之條件下呈惰性。術語"惰 性”意謂所關注之固體細粉狀研磨劑c不被本發明之拋光劑 之其他組份及待拋光材料之化學作用及拋光期間之機械作 用’尤其在壓力下之剪切力部分或完全破壞。 較佳地’有機及無機材料C係選自由下列各物組成之 群：固體元素，尤其金屬及碳；硼化物；碳化物；氮化 物；碟化物；氧化物；硫化物；及聚合物，尤其聚苯乙 烯、聚（曱基）丙烯酸酯、聚氯乙烯、聚偏二氯乙烯、聚偏 二氟乙烯、聚四氟乙烯及聚醯胺。 最佳地’無機材料C為氧化物C。 特定言之’氧化物C係選自由煙霧狀二氧化矽、膠態二 氧化發、煙霧狀氧化鋁、膠態氧化鋁、氧化鈽、二氧化鈦 及二氧化鍅組成之群，尤其選自煙霧狀二氧化矽、膠態二 氧化矽及煙霧狀氧化鋁。 本發明之拋光方法之水性拋光劑及本發明之拋光劑可含 131776.doc 200911970 有廣泛變化量之固體細粉狀研磨劑c。因此，該等量可經 極佳調整並適合於個別情況之要求。較佳地，拋光劑含有 1重量％至15重量％、最佳1重量％至1〇重量％且尤其1重量 %至5重量％之固體細粉狀研磨劑c，各值以所關注之完整 拋光劑之重量計。 本發明之拋光方法之水性拋光劑及本發明之拋光劑可含 有至少一種添加劑D。 較佳地’該添加劑D係選自通常CMP或CMP漿料之水性 抛光劑中所用之添加劑之群。 最佳地’添加劑D係選自由有機酸與無機酸及有機鹼與 無機驗、pH值緩衝劑、表面活性化合物及流變改質劑組成 之群。尤其使用無機礦物酸。尤其較佳係使用硝酸。 較佳地’選自酸、鹼及pH值緩衝劑之群之添加劑d以使 得得到3至8、尤其4至7之ΡΗ值的量含於本發明之拋光方法 之水性拋光劑及本發明之拋光劑中。 本發明之拋光方法之水性拋光劑及本發明之拋光劑之製 備並不展現任何特殊性，但可藉由溶解或分散上述組份A 及B及視情況C及/或D(本發明之拋光方法之水性拋光劑）或 A、B及C及視情況D(本發明之拋光劑）來進行。基於此目 的，可使用習用及標準混合方法及混合裝置，諸如攪拌容 、超音波混合器、均質器Preferably, the solid finely divided abrasive C is selected from the group consisting of organic and inorganic materials which are inert under CMP conditions. The term "inert" means that the solid fine powdered abrasive c of interest is not subjected to the chemical action of the other components of the polishing agent of the present invention and the material to be polished and the mechanical action during polishing, especially under pressure. Partial or complete destruction. Preferably, 'organic and inorganic material C is selected from the group consisting of solid elements, especially metals and carbon; boride; carbides; nitrides; dishings; oxides; sulfides; And polymers, especially polystyrene, poly(decyl) acrylate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene and polyamine. The best 'inorganic material C is Oxide C. In particular, the 'oxide C series is selected from the group consisting of aerosol-like cerium oxide, colloidal oxidized hair, aerosolized alumina, colloidal alumina, cerium oxide, titanium dioxide and cerium oxide, especially From aerosolized cerium oxide, colloidal cerium oxide and smoky alumina. The aqueous polishing agent of the polishing method of the present invention and the polishing agent of the present invention may contain 131776.doc 200911970, a widely varying amount of solid fine powder Grinding agent c. Therefore, the same amount can be adjusted very well and is suitable for individual cases. Preferably, the polishing agent contains from 1% by weight to 15% by weight, optimally from 1% by weight to 1% by weight and especially 1 The solid fine powder abrasive c is from 5% by weight to 5% by weight, and each value is based on the weight of the entire polishing agent of interest. The aqueous polishing agent of the polishing method of the present invention and the polishing agent of the present invention may contain at least one additive D. Preferably, the additive D is selected from the group of additives used in aqueous polishing agents for conventional CMP or CMP slurries. [Optimizedly, the additive D is selected from the group consisting of organic and inorganic acids and organic bases and inorganic tests, pH values. a group of buffers, surface-active compounds and rheology modifiers, especially inorganic mineral acids. It is especially preferred to use nitric acid. Preferably, the additive d is selected from the group consisting of acids, bases and pH buffers to An amount of from 3 to 8, especially from 4 to 7, is obtained in the aqueous polishing agent of the polishing method of the present invention and the polishing agent of the present invention. The aqueous polishing agent of the polishing method of the present invention and the preparation of the polishing agent of the present invention Does not show any special Specificity, but by dissolving or dispersing the above components A and B and optionally C and/or D (the aqueous polishing agent of the polishing method of the present invention) or A, B and C and optionally D (polishing according to the invention) For this purpose, conventional and standard mixing methods and mixing devices such as mixing capacity, ultrasonic mixer, homogenizer can be used.
131776.doc 器、串聯溶解器、高剪切力葉輪 噴嘴或逆流混合器。較佳地，將 -22- 200911970 本發明之拋光方法之水性抛光劑及本發明之拋光劑係用 於材料之最多樣性圖案化及非結構化、尤其圖案化表面之 拋光、較佳係CMP。 較佳地，材料之圖案化表面係關於金屬圖案及金屬-介 電質圖案。表佳地，金屬圖案及金屬_介電質圖案含有至 少一種、尤其一種選自由如上文所定義之金屬河及其合金 組成之群的金屬材料或由其組成。尤其使用銅作為金屬 Μ。 可使用通常使用之有機及無機介電質作為介電質。合適 介電質之實例係自歐洲專利申請案Ep i 3〇6 415八2第4頁 第[0031]段已知’該申請案之揭示内容以引用的方式包括 在本文中。詳言之，使用二氧化矽作為介電質。 詳^之，金屬_介電質圖案係關於製造具有丨匸之晶圓之 銅鑲嵌方法中所用的銅_介電質圖案。 斥如此項技術中所已知，金屬_介電質圖案、尤其銅-介電 質圖案可含有通常所用之障壁層。合適障壁層之實例自歐 2專利申請案EP i 306 4 1 5 A2第4頁第[〇〇32]段已知，該申 請案之揭示内容以引用的方式包括在本文中。 本發月之抛光方法無展現特殊性，但可用通常用於製造 具有ic之晶圓中之CMp的方法及設備來進行。 如此項技術中所已知，用於CMp之典型設備由覆蓋有拋 2之旋轉壓板組成。晶圓以其上面朝下面向拋光塾之方 :女裝於載體或夾盤上。該载體在水平位置緊固晶圓。拋 "及固持I置之此特定配置亦稱為硬壓板設計。载體可保 131776.doc •23- 200911970 持位於載體之保持表面 墊。此墊可作為用於晶 與晶圓之不拋光之表 圓之緩衝墊。 面之間的載體 在载體下方，較大直 拋光晶圓平行之表面。 圓表面。在拋光過程期 光劑或本發明之拋光劑 上0 t壓板亦通常水平安置且提供與待 其拋光墊在平坦化過程期間接觸晶 間，將本發明之拋光方法之水性拋 以連續流或逐滴方式塗覆於拋光墊 使載體與壓板兩者繞其自載體及壓板垂直延伸之各自轴 旋轉。旋轉«軸可相對於旋轉壓板㈣較於適當位置 或可相料壓板水平振盪。載體之旋轉方向通常（儘管不 -定則板之旋轉方向相同。載體及塵板之旋轉速度通 常（儘管不一定）設置為不同值。 通系，壓板之溫度設置為介於丨與7(rc之間的溫度。 欲知詳情’請參考國際專利申請案w〇 2004/0633〇1 A1，其揭示内容、尤其第16頁第[〇〇36]段至第18頁第 [0040]段以及圖1以引用的方式包括在本文中。 藉助於本發明之拋光方法及本發明之拋光劑，可獲得具 有優良功能性之具有包含銅鑲嵌圖案之1(：的晶圓。 實例及比較實例 實例1 CMP漿料中之D·葡糖胺之雙功能性以及一 1.1 CMP漿料中之D-葡糖胺之鈍化或膜構成能力al D-葡糖胺之鈍化能力al藉由測定銅盤之靜態蝕刻速率 (SER)來說明。用以下程序測定SER。最初將銅盤調節， I3I776.doc -24- 200911970 洗務’乾燥且接著稱重，隨後進行各實驗。藉由用包含膠 態二氧化矽及硝酸鐵之漿料拋光30秒來調節銅盤。接著藉 由一對經鐵氟龍（Teflon)覆蓋之夾鉗固持銅盤以減少污染 且接著直接將其浸沒於經攪拌CMP漿料中。在各種情況下 浸沒之時間為5分鐘。蝕刻後，用去離子水清洗銅盤，接 著用異丙醇沖洗。之後，用穩態加壓空氣流乾燥銅盤，且 使用以下計算法基於圓盤之淨重量損失及表面積來計算 SER : SER=重量損失/[密度x(圓周面積+2χ橫截面之面積卜時 間]， ^ 其中 重量損失=溶解後銅盤之重量損失； 密度=銅之密度； 橫截面之面積=圓盤之橫截面面積； 圓周面積=圓盤之圓周面積；且 時間=溶解時間。 CMP漿料之化學組成及其SER呈現於表}中 131776.doc -25- 200911970131776.doc, tandem dissolver, high shear impeller nozzle or countercurrent mixer. Preferably, the aqueous polishing agent of the polishing method of the present invention and the polishing agent of the present invention are used for the most diverse patterning and unstructuring of materials, especially for patterning surfaces, preferably CMP. . Preferably, the patterned surface of the material is related to the metal pattern and the metal-dielectric pattern. Preferably, the metal pattern and the metal-dielectric pattern contain or consist of at least one metal material selected from the group consisting of metal rivers and alloys thereof as defined above. Copper is especially used as the metal crucible. The commonly used organic and inorganic dielectrics can be used as the dielectric. An example of a suitable dielectric is known from the European Patent Application Ep i 3 〇 6 415 八 八 page 4 [0031] The disclosure of this application is hereby incorporated by reference. In detail, cerium oxide is used as the dielectric. In detail, the metal-dielectric pattern is a copper-dielectric pattern used in a copper damascene method for fabricating a wafer having germanium. As is known in the art, metal-dielectric patterns, especially copper-dielectric patterns, can contain barrier layers that are commonly used. Examples of suitable barrier layers are known from the European Patent Application EP 1 306 4 1 5 A2, page 4, paragraph [〇〇32], the disclosure of which is incorporated herein by reference. The polishing method of this month does not exhibit particularity, but can be carried out by a method and apparatus commonly used to manufacture CMp in wafers having ic. As is known in the art, a typical apparatus for CMp consists of a rotating platen covered with a throw. The wafer is polished to the side with the top side facing down: the woman is on the carrier or the chuck. The carrier secures the wafer in a horizontal position. This particular configuration of throwing " and holding I is also known as hard platen design. The carrier can be protected. 131776.doc •23- 200911970 Hold the surface pad on the carrier. This pad can be used as a cushion for wafers that do not polish the wafer. The carrier between the faces is below the carrier and the surface of the wafer is paralleled with a large straight diameter. Round surface. The 0 t platen is also disposed horizontally during the polishing process or the polishing agent of the present invention and is provided to contact the intergranular phase during the planarization process with the polishing pad to be polished, and the water of the polishing method of the present invention is thrown into a continuous flow or The drop pattern is applied to the polishing pad to rotate both the carrier and the platen about their respective axes extending perpendicularly from the carrier and the platen. The rotary «axis can oscillate horizontally relative to the rotating platen (4) compared to the appropriate position or the phased platen. The direction of rotation of the carrier is usually (although not the same direction of rotation of the plate. The rotational speed of the carrier and the dust plate is usually (although not necessarily) set to a different value. By the system, the temperature of the platen is set to be between 丨 and 7 (rc Temperatures. For details, please refer to International Patent Application No. 2004/0633〇1 A1, the disclosure of which, in particular, page 16 [〇〇36] to page 18, paragraph [0040] and Figure 1 By way of reference, it is included herein. By means of the polishing method of the present invention and the polishing agent of the present invention, a wafer having a copper mosaic pattern of 1 (:) having excellent functionality can be obtained. Examples and Comparative Examples Example 1 CMP Bifunctionality of D·glucosamine in the slurry and passivation or film formation ability of D-glucosamine in a 1.1 CMP slurry. Passivation ability of al D-glucosamine by measuring the static etching rate of the copper disk (SER) to illustrate. The SER was determined by the following procedure. The copper disk was initially adjusted, I3I776.doc -24- 200911970 Washing 'dry and then weighed, followed by each experiment. By using colloidal cerium oxide and ferric nitrate The slurry is polished for 30 seconds to adjust the copper plate The copper disk is then held by a pair of Teflon-coated tongs to reduce contamination and then directly immersed in the agitated CMP slurry. The immersion time is 5 minutes in each case. After etching, The copper disk was rinsed with deionized water, followed by isopropyl alcohol. Thereafter, the copper disk was dried with a steady stream of pressurized air and the SER was calculated based on the net weight loss and surface area of the disk using the following calculation: SER = weight loss / [density x (circumference area + 2 面积 cross-sectional area b time], ^ where weight loss = weight loss of copper disk after dissolution; density = density of copper; area of cross section = cross-sectional area of disk; circumference area = disk Circumference area; and time = dissolution time. The chemical composition of CMP slurry and its SER are presented in Table} 131776.doc -25- 200911970
表1 : CMP漿料第Cl號（比較）及第1至4號（實例）之組成及 其SER CMP漿料 編號 組份/重量％ 甘胺酸 h2o2 D-葡糖胺 pH值 SER/nm/min C1 0.5 1 - 5 150 1 0.5 1 0.25 5 110 2 0.5 1 0.5 5 85 3 0.5 1 0.75 5 50 4 0.5 1 1 5 35 SER隨D-葡糖胺濃度之增加而顯著減小證明D-葡糖胺之 鈍化能力a 1。 I·2 CMP漿料中之D-葡糖胺之錯合能力a2 D-葡糖胺之錯合能力藉由測定銅盤之材料移除速率 (MRR)來證明。再次，將銅盤調節（如之前所闡明），洗 滌，乾燥且接著稱重，隨後進行各實驗。之後，將其連接 於不鑛鋼載體上且接著安裝於單面拋光機（Struers Labopol-5 Grinding Table and Struers LaboForce Arm, Westlake，Ohio)上。對於該等實驗使用聚胺基甲酸酯ic 1400拋光墊。於41.37 kPa(6 psi)之壓力下藉由於墊上以 120毫升/分鐘之速率供應各CMp漿料將銅盤拋光5分鐘。 銅盤及墊具有150 rpm之相對旋轉速度。用金剛石粒度調 節劑調節該墊以移除化學反應之產物且使得墊易於進行下 -操作。拋光後’用去離子水清洗盤，接著用異丙醇沖 洗之後用加壓空氣流乾燥盤，且根據計算法基於 拋光表面積之淨重量損失來計算MRR : 、 131776.doc •26- 200911970 MRR=重量損失/(密度χ橫截面之面積χ時間）； 其中 重量損失=拋光後銅盤之重量損失； 密度=銅之密度； 橫截面之面積=盤之橫截面面積；且 時間=抛光時間。 MRR之單位通常以奈米/分鐘（nm/min)或埃/分鐘（A/min) . 量測。 ί 所用CMP漿料之材料組成及其MRR可見於表2中。Table 1: Composition of CMP slurry No. Cl (comparative) and Nos. 1 to 4 (example) and its SER CMP slurry numbering component/weight % glycine acid h2o2 D-glucosamine pH SER/nm/ Min C1 0.5 1 - 5 150 1 0.5 1 0.25 5 110 2 0.5 1 0.5 5 85 3 0.5 1 0.75 5 50 4 0.5 1 1 5 35 SER Significantly decreases with increasing D-glucosamine concentration Proof D-glucose The passivation ability of the amine a 1 . The mismatching ability of D-glucosamine in I.2 CMP slurry The mismatching ability of a2D-glucosamine was demonstrated by measuring the material removal rate (MRR) of the copper disk. Again, the copper pan was conditioned (as previously explained), washed, dried and then weighed, followed by each experiment. Thereafter, it was attached to a non-mineral steel carrier and then mounted on a single-sided polishing machine (Struers Labopol-5 Grinding Table and Struers Labo Force Arm, Westlake, Ohio). A polyurethane ic 1400 polishing pad was used for these experiments. The copper disk was polished for 5 minutes at a pressure of 41.37 kPa (6 psi) by supplying each CMp slurry at a rate of 120 ml/min on the pad. The copper disc and pad have a relative rotational speed of 150 rpm. The pad is conditioned with a diamond particle size modifier to remove the chemical reaction product and to make the pad easy to perform the down-operation. After polishing, the disk was rinsed with deionized water, then rinsed with isopropanol and then dried with a stream of pressurized air, and the MRR was calculated based on the net weight loss of the polished surface area according to the calculation: 131776.doc •26- 200911970 MRR= Weight loss / (density χ cross-sectional area χ time); where weight loss = weight loss of polished copper disk; density = density of copper; area of cross section = cross-sectional area of the disk; and time = polishing time. The unit of MRR is usually measured in nanometers per minute (nm/min) or angstroms per minute (A/min). ί The material composition of the CMP slurry used and its MRR can be found in Table 2.
表2 : CMP漿料第C2號及第C3號（比較）及第5號至第I2號 (實例）之組成及其MRR CMP漿料組份/重量％ 編號 研磨劑 H2〇2 D-葡糖胺 pH MRR/nm/min C2 氧化鋁a) 3 3 4 200 5 3 3 0.25 4 500 6 3 3 0.5 4 1750 7 3 3 0.75 4 2250 8 3 3 1 4 3450 C3 二氧化矽1^ 3 3 4 <50 9 3 3 0.25 4 150 10 3 3 0.5 4 350 11 3 3 0.75 4 900 12 ---~--- 3 3 1 4 1600 a)氧化鋁Baikalox CR-30 ; 131776.doc -27- 200911970 b)Degussa 之 Aerosil® 130 〇 因此，MRR隨D-葡糖胺量之增加而增加證實CMP漿料中 之D-葡糖胺之錯合能力a2。 D-葡糖胺之錯合能力a2亦使用Bruker Avance 400NMR藉 由D2〇之弛緩時間（Ή)來說明。為此目的，將2〇 ρριη及4〇 ppm Cu2+離子添加至溶液第C4號及第C5號（比較）及第13號 (實例）中之每一者中： C4 D20 ； C5 D2〇+1重量％之甘胺酸；且 13 〇2〇+1重量％之甘胺酸+ 1重量％之D-葡糖胺。 由於添加Cu2 +離子，因此d2〇之弛緩時間（T1)自11.5秒（0 ppm ;第以號）減少至3秒（20 ppm)至2秒（40 ppm)，該減少 表明〇2〇與Cu2+離子之錯合作用。與此相反，溶液第C5號 及第1 3號展現〇2〇之弛緩時間（τ丨）之減少顯著較低： C5. 12 秒（〇ppm) 6.5秒（20 ppm) 4 秒（40 ppm); 13. 13 秒（〇ppm) 6.5 秒（20 ppm) 5 秒（40 ppm)。 此證實含有Cu2 +之溶液第C5號及第丨3號由於甘胺酸及D_ 葡糖胺之強錯合能力a2而不含Cu2+-D20錯合物。 此外，錯合能力a2亦於UV_可見光（uv_vis)二極體陣列光 D曰光度什上使用羥基自由基（.〇H)截獲實驗來證明。證明 Cu2+-胺基酸錯合物於分解過氧化氫以得職基自由基中之 催化作用。作為比過氧化氫強的多之氧化劑之羥基自由基 立曰強在CMP期間銅於基於過氧化氯之cMp浆料中的mrr。 使用對亞硝基二甲基笨胺（PNDA)作為㈣自由基截獲劑 131776.doc -28. 200911970 來監測在Cu2+離子及胺基酸存在下羥基自由基由過氧化氯 之產生。使用UV-vis光譜法監測PNDA於各種含有過氧化 氫之測試溶液中之吸收強度。 PNDA於440 nm處具有特徵吸收峰。其與羥基自由基之 加合物於相同波長下具有弱的多之吸收峰。因此吸收強度 與所產生之羥基自由基之量反相關。PNDA強度愈小意謂 所產生之經基自由基愈多。將PNDA之初始濃度定為 0.0415 mM。使所有測試溶液第C6號至第C9號（比較）及第 14號及第15號（實例）保持在PH=6下。 進行羥基自由基截獲實驗，且根據以下等式計算含有不 同過氧化物之溶液中之準一級速率常數（pseudo_first_〇rder rate constant)及初始羥基自由基濃度： k=k'[-OH]； 其中 k=上文所示之曲線之初始斜率；且 k'=速率常數=於 21〇C 下 1.25±0.2χ10 丨 0/m〇l s ; W*M.Hariharaputhiran，J.Zhang，S.Ramajaran，J. J. Keleher ’ Yuzhuo Li及 S. V. Babu 公開於 the Journal of The Electrochemical Society，第 147 卷（10),第 3820-3826 頁 ’ 2000 中之文早”HydroxylRadicalFormationinH202-Table 2: Composition of CMP slurry Nos. C2 and C3 (comparative) and No. 5 to No. 12 (example) and its MRR CMP slurry component/% by weight No. abrasive H2〇2 D-glucose Amine pH MRR/nm/min C2 Alumina a) 3 3 4 200 5 3 3 0.25 4 500 6 3 3 0.5 4 1750 7 3 3 0.75 4 2250 8 3 3 1 4 3450 C3 Ceria 1^ 3 3 4 < ;50 9 3 3 0.25 4 150 10 3 3 0.5 4 350 11 3 3 0.75 4 900 12 ---~--- 3 3 1 4 1600 a) Alumina Baikalox CR-30 ; 131776.doc -27- 200911970 b ) Aerosil® 130 of Degussa Thus, an increase in the MRR with an increase in the amount of D-glucosamine confirms the mismatching ability a2 of D-glucosamine in the CMP slurry. The mismatching ability a2 of D-glucosamine was also illustrated by the Bruker Avance 400 NMR by the relaxation time (Ή) of D2〇. For this purpose, 2〇ρριη and 4〇ppm Cu2+ ions are added to each of the solutions C4 and C5 (comparative) and 13 (example): C4 D20 ; C5 D2〇+1 weight % of glycine; and 13 〇 2 〇 + 1% by weight of glycine + 1% by weight of D-glucosamine. Due to the addition of Cu2+ ions, the relaxation time (T1) of d2〇 was reduced from 11.5 seconds (0 ppm; number) to 3 seconds (20 ppm) to 2 seconds (40 ppm), indicating a decrease in 〇2〇 and Cu2+. The wrong combination of ions. In contrast, solutions C5 and No. 13 showed a significant decrease in the relaxation time (τ丨) of 〇2〇: C5. 12 seconds (〇ppm) 6.5 seconds (20 ppm) 4 seconds (40 ppm) 13. 13 seconds (〇ppm) 6.5 seconds (20 ppm) 5 seconds (40 ppm). It was confirmed that the solutions containing Cu2+, Nos. C5 and No. 3, did not contain the Cu2+-D20 complex due to the strong mismatching ability a2 of glycine and D_glucosamine. In addition, the mismatching ability a2 was also demonstrated by using a hydroxyl radical (.〇H) interception experiment on the UV-visible (uv_vis) diode array light. It is proved that the Cu2+-amino acid complex catalyzes the decomposition of hydrogen peroxide to obtain a radical. The hydroxyl radical, which is a much stronger oxidizing agent than hydrogen peroxide, is relatively strong in copper during the CMP during mrr in the chlorine peroxide-based cMp slurry. The use of p-nitrosodimethylamine (PNDA) as the (iv) radical trapping agent 131776.doc -28. 200911970 was used to monitor the generation of hydroxyl radicals from chlorine peroxide in the presence of Cu2+ ions and amino acids. The absorption intensity of PNDA in various test solutions containing hydrogen peroxide was monitored using UV-vis spectroscopy. PNDA has a characteristic absorption peak at 440 nm. Its adduct with hydroxyl radicals has a weak absorption peak at the same wavelength. Therefore, the absorption intensity is inversely related to the amount of hydroxyl radicals produced. The smaller the PNDA intensity means the more radical radicals are produced. The initial concentration of PNDA was set at 0.0415 mM. All test solutions Nos. C6 to C9 (comparative) and Nos. 14 and 15 (example) were kept at pH=6. Carrying out a hydroxyl radical trapping experiment, and calculating a pseudo first-order rate constant and an initial hydroxyl radical concentration in a solution containing different peroxides according to the following equation: k=k'[-OH]; Where k = the initial slope of the curve shown above; and k' = rate constant = 1.25 ± 0.2 χ 10 丨 0 / m 〇 ls at 21 ° C; W * M. Hariharaputhiran, J. Zhang, S. Ramajaran, JJ Keleher 'Yuzhuo Li and SV Babu are published in the Journal of The Electrochemical Society, vol. 147 (10), pp. 3820-3826 'in the early 2000s' Hydroxyl RadicalFormationin H202-
Amino Acid Mixtures and Chemical Mechanical Polishing of Copper"所詳述。 有關資料可見於表3中。其證明在D-葡糖胺之情況下 Cu2+-胺基酸錯合物亦產生羥基自由基，從而表明D_葡糖 131776.doc •29· 200911970 胺之錯合能力a2。 表3:含有不同過氧化氫之溶液中之準一級速率常數k及初 始經基自由基濃度 溶液 編號 組成/重量％ kxlO31/min T=21°C (OH)xl014/M T=21°C C6 PNDA 0.08 0.01 C7 PNDA+3 H2〇2 1.78 0.3 C8 PNDA+3 H2〇2+2 D-葡糖胺 1.48 0.2 14 PNDA+3 H202+2 D-葡糖胺 +100 ppm Cu2+ 8.4 1.2 15 PNDA+3 H202+2D-葡糖胺 +200 ppm Cu2+ 11.3 1.55 C9 PNDA+3 H202+1 甘胺酸 +200 ppm Cu2+ 20.7 2.7 實例2 用含有D-葡糖胺及二氧化矽或氧化鋁研磨劑之CMP漿料拋 光20.32 cm(8”）銅毯覆式晶圓 於裝備有 Rodel 1C 1000 及 Suba-IV K-槽墊之Westech 372M上使用含有下列各物之CMP漿料： -3重量％之獲自不同供應商之氧化鋁研磨劑、3重量％之 過氧化氫及0.5重量％之D-葡糖胺，各值以所關注之CMP 漿料之完整重量計，或 -變化量之二氧化石夕研磨劑（來自Degussa之Aerosil™ 13 0)、變化量之過氧化氫及變化量之D-葡糖胺。拋光條 件如下： 131776.doc -30· 200911970 -向下力：13.79 kPa(2 psi); -背壓力：6.89 kPa(l psi); -平台/載體速度：75/65 rpm ;且 -流動速率：200 ml/min。 拋光後，使用Prometrix RS 35，一種四點探針薄層電阻 工具來量測經拋光之銅毯覆式晶圓之厚度。使用 Horizon，一種無觸點光學表面輪廓儀來評估經拋光之銅 毯覆式晶圓之表面品質。 CMP漿料之材料組成及MRR及由此獲得之WIWNU展示 於表4中。所獲得之資料清楚地證明D-葡糖胺為用於銅 CMP之可行選擇。 131776.doc -31 - 200911970Amino Acid Mixtures and Chemical Mechanical Polishing of Copper" The relevant information can be found in Table 3. It is proved that in the case of D-glucosamine, the Cu2+-amino acid complex also generates hydroxyl radicals, thereby indicating D_glucose 131776.doc •29·200911970 Amine mismatching ability a2. Table 3: Quasi-first-order rate constant k and initial radical-based radical concentration in solution containing different hydrogen peroxide solution No. composition/weight% kxlO31/min T=21°C (OH)xl014/MT=21°C C6 PNDA 0.08 0.01 C7 PNDA+3 H2〇2 1.78 0.3 C8 PNDA+3 H2〇2+2 D-glucosamine 1.48 0.2 14 PNDA+3 H202+2 D-glucosamine +100 ppm Cu2+ 8.4 1.2 15 PNDA+3 H202 +2D-glucosamine +200 ppm Cu2+ 11.3 1.55 C9 PNDA+3 H202+1 Glycine +200 ppm Cu2+ 20.7 2.7 Example 2 CMP slurry containing D-glucosamine and ceria or alumina abrasive Polished 20.32 cm (8") copper blanket wafers were used on Westech 372M equipped with Rodel 1C 1000 and Suba-IV K-slot mats using CMP slurries containing: -3 wt% from different supplies Alumina abrasive, 3% by weight of hydrogen peroxide and 0.5% by weight of D-glucosamine, each value based on the total weight of the CMP slurry of interest, or - varying amounts of dioxide dioxide abrasive (AerosilTM 13 0 from Degussa), varying amounts of hydrogen peroxide and varying amounts of D-glucosamine. Polishing conditions are as follows: 131776.doc -30· 200911970 - Downforce: 13 .79 kPa (2 psi); - Back pressure: 6.89 kPa (l psi); - Platform/carrier speed: 75/65 rpm; and - Flow rate: 200 ml/min. After polishing, use Prometrix RS 35, a four Point probe thin layer resistance tool to measure the thickness of polished copper blanket wafer. Horizon, a non-contact optical surface profilometer was used to evaluate the surface quality of polished copper blanket wafers. The material composition and MRR of the material and the WIWNU obtained therefrom are shown in Table 4. The information obtained clearly demonstrates that D-glucosamine is a viable option for copper CMP. 131776.doc -31 - 200911970
表4 : CMP漿料第16號至第24號之組成及MRR及由此獲得 之 WIWNU CMP組成/重量％ 漿料研磨劑 編號 H202 D-葡糖胺 pH MRR/A/min WIWNU/% 氧化鋁 16 3EKC CU150 3 0.5 4 3800 15 17 3 Baikalox CR-30 3 0.5 4.35 5910 9 18 Ferro SRS120 3 0.5 4.75 4170 9 Aerosil™ 130 19 3 3 1.5 5 13,750 - 20 3 3 1.5 6 11,800 21 3 3 1.5 7 10,400 - 22 3 3 1.25 6 6200 - 23 3 3 1.125 6 3450 - 24 2 4 1.125 7 2400 _ 實例3 用含有D-葡糖胺及二氧化矽或氧化鋁研磨劑之CMP漿料拋 光20.32 cm(8")銅圖案化晶圓 將Sematech 854銅圖案化晶圓於裝備有Rodel 1C 1000及 Suba-IV K-槽墊之Westech 372M上進行拋光。拋光條件如 下： -向下力：13.79 kPa(2 psi); -背壓力：6.89 kPa(l psi); -平台/載體速度：75/65 rpm;且 131776.doc -32- 200911970 -流動速率：200 ml/min。 拋光後，使用Prometrix RS 35，一種四點探針薄層電阻 工具來量測經拋光之銅毯覆式晶圓之厚度。使用Ambios XP2表面輪廓儀量測階梯高度。CMP漿料之組成如下： CMP漿料第25號： 3重量％之氧化鋁（Baikalox CR-30)、3重量％之過氧化氫 及0.5重量％2D-葡糖胺，各值以CMP漿料之完整重量計， ρΗ=4·3。 ί CMP漿料第26號： 3重量％之AerosilTM 130、3重量。/〇之過氧化氫及1.25重量 %之D-葡糖胺，各值以CMP漿料之完整重量計，pH=6。 由CMP漿料第25號獲得之階梯高度彙編於表5中。由 CMP漿料第26號獲得之階梯高度彙編於表6中。 表5:由CMP漿料第25號獲得之銅圖案化測試晶圓之階梯 高度 拋光 厚度 階梯高度1〇〇_1〇〇 階梯高度50_50Table 4: Composition of CMP slurry Nos. 16 to 24 and MRR and WIWNU CMP composition/weight % obtained therefrom Slurry Abrasive No. H202 D-Glucosamine pH MRR/A/min WIWNU/% Alumina 16 3EKC CU150 3 0.5 4 3800 15 17 3 Baikalox CR-30 3 0.5 4.35 5910 9 18 Ferro SRS120 3 0.5 4.75 4170 9 AerosilTM 130 19 3 3 1.5 5 13,750 - 20 3 3 1.5 6 11,800 21 3 3 1.5 7 10,400 - 22 3 3 1.25 6 6200 - 23 3 3 1.125 6 3450 - 24 2 4 1.125 7 2400 _ Example 3 Polishing 20.32 cm (8") with a CMP slurry containing D-glucosamine and cerium oxide or alumina abrasive Copper patterned wafers were polished on Sematech 854 copper patterned wafers on a Westech 372M equipped with Rodel 1C 1000 and Suba-IV K-slot mats. Polishing conditions are as follows: - downward force: 13.79 kPa (2 psi); - back pressure: 6.89 kPa (l psi); - platform / carrier speed: 75/65 rpm; and 131776.doc -32 - 200911970 - flow rate: 200 ml/min. After polishing, the thickness of the polished copper blanket wafer was measured using a Prometrix RS 35, a four-point probe sheet resistance tool. The step height was measured using an Ambios XP2 surface profiler. The composition of the CMP slurry is as follows: CMP slurry No. 25: 3% by weight of alumina (Baikalox CR-30), 3% by weight of hydrogen peroxide and 0.5% by weight of 2D-glucosamine, each value being CMP slurry The complete weight, ρΗ=4·3. ί CMP slurry No. 26: 3 wt% AerosilTM 130, 3 weight. / hydrazine hydrogen peroxide and 1.25 wt% D-glucosamine, each value based on the total weight of the CMP slurry, pH = 6. The step height obtained from CMP slurry No. 25 is compiled in Table 5. The step height obtained from CMP slurry No. 26 is compiled in Table 6. Table 5: Steps for copper patterned test wafers obtained from CMP slurry No. 25 Height Polishing Thickness Step height 1〇〇_1〇〇 Step height 50_50
時間/s /A 晶粒1 晶粒2 晶粒3 晶粒1 晶粒2 晶粒3 0 10,500 5100 5000 4900 5100 5000 4900 60 4500 260 120 240 190 95 220 90 1200 n/a n/a n/a n/a n/a n/a 105 0 -270 -235 -150 -250 -350 -180 n/a不可用 131776.doc -33- 200911970 表6:由CMP漿料第26號獲得之銅圖案化測試晶圓之階梯 南度 抛光 晶粒1 晶粒2 晶粒3 晶粒4 晶粒5 時間/s Th./A S.H./A Th./A S.H./A Th./A S.H./A Th./A S.H./A Th./A S.H./A 0 10,800 4160 10,800 5110 10,800 5000 10,800 4980 10,800 5020 40 8400 2900 6300 1100 6200 625 5600 n/a 5300 n/a 60 7500 2100 4900 n/a 4550 n/a 3950 n/a 3600 n/a 90 6200 1400 1550 n/a 1300 n/a 800 n/a 0 -575 110 5000 1100 0 -455 0 -650 0 -980 0 -1650 n/a不可用；Time / s /A Grain 1 Grain 2 Grain 3 Grain 1 Grain 2 Grain 3 0 10,500 5100 5000 4900 5100 5000 4900 60 4500 260 120 240 190 95 220 90 1200 n/an/an/an/an /an/a 105 0 -270 -235 -150 -250 -350 -180 n/a not available 131776.doc -33- 200911970 Table 6: Steps for copper patterned test wafers obtained from CMP slurry No. 26 Southern Polished Grain 1 Grain 2 Grain 3 Grain 4 Grain 5 Time / s Th./A SH/A Th./A SH/A Th./A SH/A Th./A SH/A Th ./A SH/A 0 10,800 4160 10,800 5110 10,800 5000 10,800 4980 10,800 5020 40 8400 2900 6300 1100 6200 625 5600 n/a 5300 n/a 60 7500 2100 4900 n/a 4550 n/a 3950 n/a 3600 n/ a 90 6200 1400 1550 n/a 1300 n/a 800 n/a 0 -575 110 5000 1100 0 -455 0 -650 0 -980 0 -1650 n/a not available;
Th.厚度； S.H.階梯高度。 所獲得之資料證明D-葡糖胺鈍化銅表面以減少諸如表面 凹陷及侵I虫之圖案化缺陷之能力a 1。 雖然本發明已結合其特定實施例加以描述，但顯然許多 替代、修改及變化形式對於熟習此項技術者而言根據上文 之描述將顯而易見。因此，在不悖離一般性發明概念之精 神或範疇之情況下可對該等細節作出改變。 131776.doc -34-Th. Thickness; S.H. Step height. The information obtained demonstrates that D-glucosamine passivates the copper surface to reduce the ability to surface defects such as surface depressions and invading insects a1. Although the invention has been described in connection with the specific embodiments thereof, it will be understood that Therefore, changes may be made to these details without departing from the spirit or scope of the general inventive concept. 131776.doc -34-
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|---|---|
| TW (1) | TW200911970A (en) |
| WO (1) | WO2008151918A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2427523B1 (en) | 2009-05-06 | 2015-10-28 | Basf Se | An aqueous metal polishing agent comprising a polymeric abrasive containing pendant functional groups and its use in a cmp process |
| EP2427522B1 (en) | 2009-05-06 | 2017-03-01 | Basf Se | An aqueous polishing agent comprising solid polymer particles and two complexing agents and its use in a process for polishing patterned and unstructured metal surfaces |
| KR101701537B1 (en) | 2009-05-08 | 2017-02-01 | 바스프 에스이 | Oxidizing particles based slurry for nobel metal including ruthenium chemical mechanical planarization |
| EP2858097B1 (en) * | 2012-05-30 | 2019-02-27 | Kuraray Co., Ltd. | Slurry for chemical mechanical polishing and chemical mechanical polishing method |
| CN103785365B (en) * | 2014-02-25 | 2016-03-30 | 南开大学 | A kind of preparation method of metalloform-selective composite membrane for separation |
| US11339308B2 (en) * | 2016-03-01 | 2022-05-24 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3397501B2 (en) * | 1994-07-12 | 2003-04-14 | 株式会社東芝 | Abrasive and polishing method |
| EP2194570A1 (en) * | 1998-12-28 | 2010-06-09 | Hitachi Chemical Co., Ltd. | Materials for polishing liquid for metal, polishing liquid for metal, mehtod for preparation thereof and polishing method using the same |
| JP2002110596A (en) * | 2000-10-02 | 2002-04-12 | Mitsubishi Electric Corp | Polishing agent for semiconductor processing, dispersant used therefor, and method of manufacturing semiconductor device using the same polishing agent |
| WO2005101474A1 (en) * | 2004-04-12 | 2005-10-27 | Hitachi Chemical Co., Ltd. | Metal polishing liquid and polishing method using it |
| EP1616926A1 (en) * | 2004-07-15 | 2006-01-18 | Interuniversitair Microelektronica Centrum ( Imec) | Slurry composition and method for chemical polishing of copper integrated with tungsten based barrier metals |
| JP4776269B2 (en) * | 2005-04-28 | 2011-09-21 | 株式会社東芝 | Metal film CMP slurry and method for manufacturing semiconductor device |
-
2008
- 2008-05-26 WO PCT/EP2008/056395 patent/WO2008151918A1/en active Application Filing
- 2008-06-09 TW TW97121442A patent/TW200911970A/en unknown
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| Publication number | Publication date |
|---|---|
| WO2008151918A1 (en) | 2008-12-18 |
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