CN100432174C - 阻挡层抛光流体 - Google Patents
阻挡层抛光流体 Download PDFInfo
- Publication number
- CN100432174C CN100432174C CNB200410011818XA CN200410011818A CN100432174C CN 100432174 C CN100432174 C CN 100432174C CN B200410011818X A CNB200410011818X A CN B200410011818XA CN 200410011818 A CN200410011818 A CN 200410011818A CN 100432174 C CN100432174 C CN 100432174C
- Authority
- CN
- China
- Prior art keywords
- polishing
- compound
- polishing fluids
- abrasive
- fluids
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005498 polishing Methods 0.000 title claims abstract description 129
- 239000012530 fluid Substances 0.000 title claims abstract description 66
- 230000004888 barrier function Effects 0.000 title claims abstract description 41
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 69
- 125000001424 substituent group Chemical group 0.000 claims abstract description 29
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 23
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 17
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 20
- 230000000903 blocking effect Effects 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000012964 benzotriazole Substances 0.000 claims description 12
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 4
- OFLXLNCGODUUOT-UHFFFAOYSA-N acetohydrazide Chemical compound C\C(O)=N\N OFLXLNCGODUUOT-UHFFFAOYSA-N 0.000 claims description 4
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- WCQOBLXWLRDEQA-UHFFFAOYSA-N ethanimidamide;hydrochloride Chemical compound Cl.CC(N)=N WCQOBLXWLRDEQA-UHFFFAOYSA-N 0.000 claims description 3
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 claims description 3
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 abstract description 19
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- 239000003153 chemical reaction reagent Substances 0.000 description 26
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- 238000012360 testing method Methods 0.000 description 18
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
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- 239000003112 inhibitor Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
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- 239000001301 oxygen Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
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- 239000002002 slurry Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000006413 ring segment Chemical group 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- 101150065749 Churc1 gene Proteins 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
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- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
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- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- LNTHITQWFMADLM-UHFFFAOYSA-M gallate Chemical compound OC1=CC(C([O-])=O)=CC(O)=C1O LNTHITQWFMADLM-UHFFFAOYSA-M 0.000 description 2
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 description 2
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- 125000005842 heteroatom Chemical group 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
- LLYCMZGLHLKPPU-UHFFFAOYSA-M perbromate Chemical compound [O-]Br(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-M 0.000 description 2
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- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
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- 150000003573 thiols Chemical class 0.000 description 2
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- AFVDZBIIBXWASR-AATRIKPKSA-N (E)-1,3,5-hexatriene Chemical compound C=C\C=C\C=C AFVDZBIIBXWASR-AATRIKPKSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
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- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
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- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
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- JXOOCQBAIRXOGG-UHFFFAOYSA-N [B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[Al] Chemical compound [B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[Al] JXOOCQBAIRXOGG-UHFFFAOYSA-N 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
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Classifications
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- 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
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/07—Fire prevention, containment or extinguishing specially adapted for particular objects or places in vehicles, e.g. in road vehicles
- A62C3/10—Fire prevention, containment or extinguishing specially adapted for particular objects or places in vehicles, e.g. in road vehicles in ships
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C35/00—Permanently-installed equipment
- A62C35/20—Hydrants, e.g. wall-hoses, wall units, plug-in cabinets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B19/00—Arrangements or adaptations of ports, doors, windows, port-holes, or other openings or covers
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- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05C—BOLTS OR FASTENING DEVICES FOR WINGS, SPECIALLY FOR DOORS OR WINDOWS
- E05C3/00—Fastening devices with bolts moving pivotally or rotatively
- E05C3/02—Fastening devices with bolts moving pivotally or rotatively without latching action
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- 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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B19/00—Arrangements or adaptations of ports, doors, windows, port-holes, or other openings or covers
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- Combustion & Propulsion (AREA)
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Abstract
该抛光流体适用于抛光半导体衬底的含钽阻挡层材料。该抛光流体包含具有至少两个氮原子的含氮化合物并且该含氮化合物包括亚胺化合物和肼化合物。该含氮化合物不含吸电子取代基;而且该抛光流体能够从半导体衬底的表面除去含钽的阻挡层材料而无需研磨剂。
Description
技术领域
本发明涉及抛光半导体衬底且更具体地,涉及去除阻挡层的无研磨剂抛光流体。
背景技术
可以通过在电介质层中布置多个沟槽来形成半导体器件的电路互连。该互连是通过在下层的电介质层上镀覆阻挡层薄膜,然后在该阻挡层薄膜上镀覆金属层形成。形成的金属层必需具有足够的厚度以便使金属充满沟槽。该互连制造工艺包括两步化学机械抛光(CMP)过程的使用。
CMP是指用抛光垫或抛光流体抛光半导体晶片的工艺。在第一步抛光中,从下层的阻挡层薄膜和下层的电介质层上除去金属层。该金属层的去除既是通过抛光垫所施加的摩擦作用,也是通过与该抛光流体的化学反应以及伴随的化学反应产物的溶解作用。第一步抛光可去除金属层,同时在晶片上留下光滑平坦的抛光表面,并进一步在沟槽中留下金属以便提供与抛光表面基本平齐的电路互连。除金属的去除以外,一些第一步抛光过程需要电介质层的去除。例如Lee等人在欧洲专利公开1 072 662 Al中公开了使用胍作为研磨加速剂用于提高研磨组合物的电介质去除速率。
典型的第一步抛光过程包括在抛光流体中使用含有氧化剂例如KNO3或H2O2的水溶液以便去除铜互连。该铜金属层的去除是通过氧化剂对金属层的氧化作用和抛光垫的研磨。此外,抛光垫磨蚀该金属层从而最大程度上减少溶解氧化物从溶液中再次沉积到被抛光材料的表面。从下层的阻挡层薄膜例如钽(Ta)或氮化钽(TaN)上去除铜。该阻挡层薄膜比铜具有更大的研磨抵抗性,因此阻挡层起到使第一步的铜抛光停止的抛光停止作用。此外,抛光流体对阻挡层薄膜表面的氧化会抑制其在第一步抛光中的去除。
在第二抛光步骤中,从下面的电介质层上去除阻挡层薄膜。第二步抛光能够在电介质层上提供光滑,平坦的抛光表面。理想情况下,该第二抛光步骤不会除去过多的沟槽中的金属。在第二抛光步骤中过度的金属去除会导致凹陷。
凹陷是描述由于除去沟槽中过多的金属从而在电路互连中形成的不需要的空穴的技术术语。凹陷既可以发生在第一步抛光中也可以发生在第二抛光步骤中。要求该电路互连具有精确的尺寸,该尺寸决定了电路互连所提供的信号传输线路的电阻。超过许可水平的凹陷会在电路互连中引起尺度缺陷,这会导致该电路互连所传输的电信号的减弱。
该第二抛光步骤应当只引起最小程度的腐蚀。腐蚀是描述由于除去阻挡层薄膜下面的一些电介质层而引起的电介质层表面的不需要的降低的技术术语。发生在接近沟槽中的金属处的腐蚀会在该电路互连中引起尺度缺陷,该缺陷会导致该电路互连所传输的电信号的减弱。为了最大程度上减小腐蚀,希望第二步抛光的抛光流体能以比电介质层的去除速率更高的去除速率去除该阻挡层薄膜。
该第二抛光步骤应具有高的阻挡层相对于下层的去除选择性。去除选择性定义为阻挡层薄膜的去除速率与相对层如电介质层或金属层的去除速率的比值。对本说明书而言,选择性是指以每单位时间的距离例如埃每分钟表示的去除速率的比值。因此,去除选择性是阻挡层薄膜相对于电介质层或金属层的去除的量度。另外,提高去除选择性可以提高抛光性能。使用表现出高的相对于电介质层的去除选择性的抛光流体进行的抛光可增加阻挡层薄膜的去除而减少电介质层的去除。
本领域浆料的情形需要较大量的研磨剂颗粒以便除去阻挡层。遗憾的是,这些浆料通常会导致无法接受的金属互连的凹陷和电介质腐蚀。鉴于这一点,对于能以高的速率去除阻挡层同时具有减小的金属互连凹陷和电介质腐蚀的阻挡层去除组合物存在持续的需求。
发明内容
本发明提供了用于抛光半导体衬底的含钽阻挡层材料的抛光流体,该流体包含:具有至少两个氮原子的含氮化合物,该含氮化合物包含至少一种选自如下式的化合物:
和肼化合物R3R4N-NR5R6(II)
其中R1包括-H或-NH2而R2,R3,R4,R5和R6独立地包括选自下列的取代基:-H,烃基,氨基,羰基,亚氨基,偶氮基,氰基,硫基,硒基和其中的R7包含烃基的-OR7,并且该含氮化合物不含吸电子取代基;该抛光流体能够无需研磨剂的从半导体衬底的表面去除含钽的阻挡层材料。
本发明的另一个方面是提供了用于抛光半导体衬底的含钽阻挡层材料的抛光流体,该流体包含:0至6wt%用于减少互连金属去除的抑制剂;0至1wt%的研磨颗粒;0至25wt%的氧化剂;0至15wt%的配位剂和0.05至25wt%具有至少两个氮原子的含氮化合物,该含氮化合物包含至少一种选自如下式的化合物:
和肼化合物R3R4N-NR5R6(II)
其中R1包括-H或-NH2而R2,R3,R4,R5和R6独立地包括选自下列的取代基:-H,烃基,氨基,羰基,亚氨基,偶氮基,氰基,硫基,硒基和其中的R7包含烃基的-OR7,并且该含氮化合物具有给电子取代基;该抛光流体能够无需研磨剂的从半导体衬底的表面除去含钽的阻挡层材料。
此外,本发明提供了对具有金属互连层和与该金属互连层相邻的含钽阻挡层的半导体衬底进行抛光的方法,该方法包括:使用抛光流体抛光阻挡层以便除去至少一部分的含钽阻挡层,该抛光流体不含研磨剂而包含具有至少两个氮原子的含氮化合物,该含氮化合物包含至少一种选自如下式的化合物:
和肼化合物R3R4N-NR5R6(II)
其中R1包括-H或-NH2;而R2,R3,R4,R5和R6独立地包括选自下列的取代基:-H,烃基,氨基,羰基,亚氨基,偶氮基,氰基,硫基,硒基和其中的R7包含烃基的-OR7,并且该含氮化合物不含吸电子取代基。
具体实施方式
在本发明的优选实施方案中,使用含氮抛光试剂例如亚胺衍生化合物或肼衍生化合物配制无研磨剂的抛光流体。
优选的亚胺衍生物包括式(I)的化合物:
其中R1是-H或-NH2而R2是-H,-NH2,烃基,氨基,羰基,亚氨基,偶氮基,氰基,硫基,或硒基和其中R7是烃基的-OR7。
优选的肼衍生物包括式(II)的化合物:
R3R4N-NR5R6(II)
且其中R3,R4,R5,和R6独立地是-H,-OR7,-NH2,烃基,羰基,亚氨基,偶氮基,氰基,硫基,或硒基。
术语“含氮”是指包含两个或多个氮原子的物质。在含氮物质中两个或多个氮原子可以互相结合,或者可以被其它原子隔开。如果含氮物质包含三个或更多的氮原子,这些氮原子其中的一些可以互相结合而其它氮原子可以只与非氮原子结合。含氮物质中的氮原子可以是该物质中的化学基团例如氨基,酰胺基,偶氮基,亚氨基,或肼基的一部分。优选地,含氮物质中的氮原子处于它们的还原态且不与氧原子直接结合(即-NO2;-NO3)。
术语“烃基”是指用氢原子取代的直链,支链或环状碳原子链,且包括未取代和取代烷基,烯基,炔基,芳基,和杂环基。优选地,烃基包含1至20个碳原子。可选地,用其它基团取代烃基。碳原子之间的结合可独立地选自单键,双键,和三键。
术语“烷基”(或烷基-)是指取代或未取代直链,支链或环状烃链,该烃链优选包含1至20个碳原子。烷基包括,例如甲基,乙基,丙基,异丙基,环丙基,丁基,异丁基,叔丁基,仲丁基,环丁基,戊基,环戊基,己基和环己基。
术语“烯基”(或烯基-)是指取代或未取代直链,支链或环状烃链,且该烃链包含至少一个碳-碳双键,且该烃链优选包含2至20个碳原子。烯基包括,例如乙烯基(-CH=CH2);1-丙稀基;2-丙稀基(或烯丙基,CH2-CH=CH2);1,3-丁二烯基(-CH=CHCH=CH2);1-丁烯基(-CH=CHCH2CH3);己烯基;戊烯基;1,3,5-己三烯基;环己二烯基;环己烯基;环戊烯基;环辛烯基;环庚二烯基;和环辛三烯基。
术语“炔基”(或炔基-)是指包含至少一个碳-碳三键的取代或未取代直链,支链或环状烃链,且该烃链优选包含2至20个碳原子。炔基包括,例如乙炔基(-C≡CH);2-甲基-3丁炔基;和己炔基。
术语“芳基”是指取代或未取代芳香碳环基,该碳环基优选包含3至20个碳原子。芳基可以是单环或者是多环。芳基包括,例如苯基,萘基,二苯基,苯甲基,甲苯基,二甲苯基,苯乙基,苯甲酸盐,烷基苯甲酸盐,苯胺,和N-烷基苯氨基。
术语“杂环基”是指包含一个或多个杂原子的饱和,非饱和,或芳香环组成部分,且该部分优选包含5至10个环上原子,且更优选包含5至6个环上原子。术语“环上原子”是指包含在环结构中的原子而不包括悬挂在该环上的其它原子。该环可以是单环,双环或多环。杂环基包含碳原子和1至3个独立地选自氮,氧,和硫的杂原子。杂环基也可以是取代或未取代的,其中包括例如苯并咪唑,苯并三唑,呋喃,咪唑,吲哚,异喹啉,异噻唑,吗啉,哌嗪,吡嗪,吡唑,吡啶,嘧啶,吡咯,喹啉,噻唑,噻吩,三嗪和三唑。
当用来描述化学基团时,术语“取代”是指包含至少一个,优选1至5个取代基的化学组成部分。适合的取代基包括,例如羟基(-OH),氨基(-NH2),氧(-O-),羰基(>C=O),硫羟基(thiol),烷基,卤素,硝基,芳基和杂环基。可选地,用1至5个取代基进一步取代这些取代基。
术语“氨基”是指通过氮原子与本体结合的基团。例如,氨基可选自如下基团:-NH2;烷基氨基(-NH-烷基);二烷基氨基(-N-(烷基)2);芳氨基(-NH-芳基)和它们的取代衍生物。优选地,与氮结合的烷基包含1至20个碳原子,而与氮结合的芳基包含3至20个碳原子。二烷基氨基中的烷基可以相同也可以不同。
术语“羰基”是指包含与氧原子双键结合的碳原子的基团,且包括羧酸,酸酐,碳酸盐,醛,酮,酯,羧酸卤化物,和酰胺。例如,羰基可以具有下面的通式(III):
其中R8是-H,-OH,-OR9,-OR10,-NH2,和-NH-C(=O)-R11,且R9,R10,和R11独立地是包含1至10个碳原子的烷基。
术语“亚氨基”是指包含与-NH基以双键结合的碳原子的基团。例如,亚氨基可以具有下面的通式(IV):
其中R12是-H,-NH2,或包含1至10个碳原子的烷基。术语“偶氮基”是指包含氮氮双键,或一个-NH基与另一个-NH基单键结合的基团。例如,偶氮基可以选自-N3;-NH-NH-NH3;-N=N-NH3;-N=N-R13;-R14=N-N=R15;和-NH-NH-R16;其中R13,R14,R15,R16独立地是包含1至10个碳原子的烷基。
术语“氰基”是指包含碳氮三键,或碳原子与氮原子双键结合并同时与另一个杂原子如氧,硫,或硒双键结合的基团。例如,氰基可以选自-C≡N;-N≡C;-N=C=O;-N=C=S;和-N=C=Se。
术语“硫基”是指包含与另一个原子单键结合的硫原子的基团。例如,硫基可以选自-S-R17;-S-S-R18;-S-C≡N;SO2H;和-SOH;其中R17和R18独立地是包含1至10个碳原子的烷基。
术语“硒基”是指包含与另一个原子单键结合的硒原子的基团。例如,硒基可以选自-Se-R19;-Se-Se-R20;-Se-C≡N;其中R19和R20独立地是包含1至10个碳原子的烷基。
优选的式(I)的亚胺衍生物包括,例如1,3-二苯胍,盐酸胍,四甲基胍,甲脒乙酸盐,和盐酸乙脒。
优选的式(II)的肼衍生物包括,例如碳酰肼,咪唑,乙酰肼,盐酸氨基脲,和甲酰肼。
式(I)的亚胺衍生化合物优选包含给电子取代基如R1或R2,而不含吸电子取代基。更优选地,R1和R2中的一个是给电子取代基,而另一个取代基是氢或者给电子取代基。如果亚胺衍生化合物中存在两个给电子取代基时,该取代基可以相同或者也可以不同。
式(II)的亚胺衍生化合物优选包含肼官能团(>N-NH2)且包含不多于一个的吸电子取代基。当R3和R4均为氢,或者当R5和R6均为氢时可提供肼官能团。
对本说明书而言,术语“给电子”是指与本体结合的且可向该本体转移电子密度的化学基团。F.A.Carey和R.J.Sundberg在AdvancedOrganic Chemistry,Part A:Structure and Mechanisms,3rd EditionNew York:Plenum Press(1990),p.208和546-561中提供了更详细的给电子取代基的描述。该亚胺衍生化合物具有能够向本体转移足够的电子密度从而在该取代基上形成可测量的局部正电荷的给电子取代基。给电子取代基包括,例如氨基,羟基(-OH),烷基,取代烷基,烃基,取代烃基,酰胺基,和芳基。这些给电子取代基可促进含钽阻挡层材料的去除。
此外,研磨添加剂可使亚胺和肼衍生化合物与吸电子取代基作用。术语“吸电子”是指与本体结合的且可以将电子密度从该本体转移出的化学基团。吸电子取代基可从本体上转移出足够的电子密度从而在该取代基上建立可测量的局部负电荷而不会促进阻挡层的去除。吸电子取代基包括,例如-O-烷基;-卤素;C(=O)H;-C(=)O-烷基;-C(=O)OH;-C(=O)-烷基;-SO2H;-SO3H;和-NO2。该吸电子的羰基不是酰胺基。
该流体中含氮抛光试剂浓度的范围可以是例如0.05至25wt%。本说明书以重量百分比表示组成,除非另外明确说明。可以使用单一类型的含氮抛光试剂,或者也可以使用含氮抛光试剂的混合物。优选地,含氮抛光试剂的浓度是0.1至10wt%。更优选地,含氮抛光试剂的浓度是1至5wt%。还要优选地,含氮抛光试剂的浓度是1.5至3wt%。在最优选的实施方案中,含氮抛光试剂的浓度是至少2wt%。
可选地,该组合物包含0至25wt%的氧化剂。优选地,该组合物包含0至15wt%的氧化剂。该氧化剂对提高互连金属如铜的去除速率尤其有效。该氧化剂可以是许多氧化剂化合物中的至少一种,例如过氧化氢(H2O2),单过硫酸盐,碘酸盐,过邻苯二甲酸镁,过乙酸,高碘酸盐,过溴酸盐,高氯酸盐,过硫酸盐,溴酸盐,硝酸盐,铁盐,铈盐,Mn(III),Mn(IV)和Mn(VI)盐,银盐,Cu盐,铬盐,钴盐,卤素,次氯酸盐和它们的混合物。此外,通常优选使用氧化剂化合物的混合物。最有利的氧化剂是过氧化氢和碘酸盐。当该抛光流体包含不稳定氧化剂例如过氧化氢时,通常最优选在使用时将该氧化剂混入浆料。由于不含氧化剂时该组合物在7以上的pH水平起作用,最优选地,该组合物不包含氧化剂以便限制金属互连例如铜的不良静态腐蚀。在低于7的pH水平,该流体需要氧化剂以便促进阻挡层的去除。
在包含余量水的溶液中,该阻挡层去除剂可以在宽的pH范围上提供效力。该溶液的有益pH范围至少为2至12。优选地,该溶液具有介于7至12之间的pH。更优选地,该溶液的pH介于8至11之间。用于降低pH的典型试剂包括硝酸,硫酸,盐酸,磷酸和有机酸。最优选地,使用氢氧化钾和硝酸提供最后的pH调节。此外,该溶液最优选依靠余量的去离子水来限制附带杂质。
用于选择性去除阻挡层的抛光流体可以在水性混合物中包含含氮抛光试剂。该抛光流体还可以选择性包含金属腐蚀配位剂,杀菌剂,和盐(例如氯化物盐如氯化铵),以及不干扰CMP工艺的其它添加剂。
适用于该互连的金属包括,例如铜,铜合金,金,金合金,镍,镍合金,铂族金属,铂族金属合金,银,银合金,钨,钨合金和包含前述金属中至少一种的混合物。优选的互连金属是铜。在使用氧化剂如过氧化氢的酸性抛光组合物和流体中,主要由于铜的氧化,铜的去除速率和静态腐蚀速率两者都较高。为了降低互连金属的去除速率,该抛光组合物使用了腐蚀抑制剂。腐蚀抑制剂的作用是减少该互连金属的去除。这可以通过减少互连金属的凹陷从而促进抛光性能的提高。
该抑制剂的典型存在量是0至6wt%——该抑制剂可以是单一的抑制剂或者是互连金属抑制剂的混合物。在这个范围内,希望抑制剂含量大于或等于0.0025wt%,优选大于或等于0.10wt%。在这个范围内还希望其含量小于或等于4wt%,优选小于或等于1wt%。优选的腐蚀抑制剂是苯并三唑(BTA)。在一个实施方案中,该抛光组合物可以包含相对大量的BTA抑制剂以便降低互连的去除速率。在大于0.25wt%的BTA浓度下,无需添加额外的腐蚀抑制剂。优选的BTA浓度是0.0025至2wt%。
可选用于该抛光流体的示例性配位剂包括乙酸,柠檬酸,乙酰乙酸乙酯,羟基乙酸,乳酸,苹果酸,草酸,水扬酸,二乙基二硫代氨基甲酸钠,丁二酸,酒石酸,疏基乙酸,甘氨酸,丙氨酸,天冬氨酸,乙二胺,三甲基二胺,丙二酸,谷氨酸(gluteric acid),3-羟基丁酸,丙酸,邻苯二甲酸,间苯二甲酸,3-羟基水杨酸,3,5-二羟基水杨酸,棓酸,葡萄糖酸,邻苯二酚,连苯三酚,棓酸,丹宁酸,和它们的盐。最优选地,该抛光流体中所用该配位剂是柠檬酸。最优选地,该抛光流体包含0至15wt%的配位剂。
虽然该含氮抛光试剂可提供有效的无研磨剂抛光流体,但是在一些应用希望向该抛光流体中添加研磨剂。该抛光组合物可选包含最高25wt%的研磨剂以便促进二氧化硅的去除或阻挡层和二氧化硅一起的去除——取决于该集成方案,该抛光组合物可用于去除掩模层或者首先去除阻挡层然后去除含氧化硅层。该抛光组合物可选包含用于“机械”去除阻挡层的研磨剂。该研磨剂优选为胶态或气相(fumed)研磨剂。研磨剂的实例包括无机氧化物,金属硼化物,金属碳化物,金属氮化物,聚合物颗粒和包含前述研磨剂其中至少一种的混合物。适合的无机氧化物包括,例如二氧化硅(SiO2),氧化铝(Al2O3),氧化锆(ZrO2),氧化铈(CeO2),氧化锰(MnO2),或包含前述氧化物其中至少一种的组合。如果需要也可以使用这些无机氧化物的改良形式,例如聚合物包覆无机氧化物颗粒和无机包覆颗粒。适合的金属碳化物,硼化物和氮化物包括,例如碳化硅,氮化硅,碳氮化硅(SiCN),碳化硼,碳化钨,碳化锆,硼化铝,碳化钽,碳化钛,或包含前述金属碳化物,硼化物,氮化物其中至少一种的组合。如果需要也可以使用金刚石作为研磨剂。可选的研磨剂还包括聚合物颗粒和包覆聚合物颗粒。优选的研磨剂是二氧化硅。
为了限制腐蚀和凹陷,研磨剂的优选用量小于5wt%。使用0至1wt%或小于1wt%的研磨剂有利于进一步限制凹陷和腐蚀。最优选地,该抛光流体不包含研磨剂以便进一步减少凹陷和腐蚀。
该研磨剂具有小于或等于150纳米(nm)的平均颗粒尺寸以便防止过度的金属凹陷和电介质腐蚀。对本说明书来说,颗粒尺寸是指该研磨剂的平均颗粒尺寸。希望使用具有小于或等于100nm的平均颗粒尺寸的胶态研磨剂,且更优选小于或等于50nm,且最优选小于或等于40nm的胶态研磨剂。当使用具有小于或等于40nm的平均颗粒尺寸的胶态二氧化硅时,可产生最少的电介质腐蚀和金属凹陷。将该胶态研磨剂的尺寸减小到小于或等于40nm时,趋向于提高该抛光组合物的选择性;但其也趋向于降低阻挡层的去除速率。此外,优选的胶态研磨剂可以包含添加剂,例如分散剂,表面活性剂和缓冲剂以便在酸性pH范围内提高该胶态研磨剂的稳定性。一种这样的胶态研磨剂是法国Clariant S.A.,Puteaux的胶态二氧化硅。该化学机械平坦化组合物还可选包含光亮剂如氯化铵,配位剂,螯合剂,pH缓冲剂,杀菌剂和消泡剂。
如果该抛光组合物不包含研磨剂,这时对于化学机械平坦化(CMP)工艺,垫的选择和调整变得更为重要。例如,对于一些无研磨剂组合物,固定研磨剂垫可改善抛光性能。
该溶液依靠阻挡层去除剂来去除含钽阻挡层材料。对本说明书而言,含钽阻挡层材料是指钼,含钽合金,钽基合金和钽的金属间化合物。该溶液对于钽,钽基合金和钽的金属间化合物例如钽的碳化物,氮化物和氧化物特别有效。对于从具有图案的半导体晶片上去除钽和氮化钽阻挡层该浆料最为有效。
在复合半导体衬底中使用的典型电介质包括SiO2,原硅酸四乙酯(TEOS),磷硅酸盐玻璃(PSG),硼硅酸盐玻璃(BPSG),或低k电介质。低k电介质包括多孔二氧化硅和有机低k电介质,例如含氟聚合物和共聚物。
希望不以高的速率去除金属从而避免凹陷。还希望不以高的速率去除电介质以便避免腐蚀。优选地,该抛光流体的阻挡层相对电介质层的去除选择性至少为10,且更优选至少为20,且还要优选的是至少50,且更为优选的是至少100。优选地,该抛光流体的阻挡层相对金属的去除选择性至少为5,且更优选至少为10,且最优选至少为15。
实施例
进行试验以便测试用于第二步抛光的抛光流体组成上的变化,该抛光通过CMP以适当的速率从半导体晶片上的下层氧化硅电介质层上去除TaN的阻挡层薄膜,并最大程度上减小电介质层的腐蚀和半导体晶片上的沟槽中金属的凹陷。使用Politex抛光垫(购自Rodel,Inc.,Network,Delaware)在3磅每平方英寸(psi)或20.7kPa的下压力条件和约200立方厘米每分钟(cc/min)的抛光流体流速下,在Strausbaugh抛光机上利用所列举的抛光流体对(200mm)半导体晶片进行抛光以测定去除速率。使用抛光垫和抛光流体,通过分别抛光氮化钽(TaN)阻挡层薄膜,原硅酸四乙酯(TEOS)电介质层和铜(Cu)金属薄膜进行试验。
在pH 9(使用氢氧化钾,硝酸和余量的去离子水调节pH)下对该抛光流体进行测试而且该抛光流体包含0.1wt%的苯并三唑(BTA)和0.01wt%的NeoloneTM M-50杀菌剂(Rohm and Haas Company,Philadelphia,Pennsylvania,USA)。腐蚀抑制剂BTA的存在可以抑制晶片上的金属的氧化。典型按供应商所规定的浓度使用该杀菌剂。该抛光流体还可以包含少量氯化铵以便抛光包含铜互连的半导体衬底。以数字表示的试验代表本发明的实施例而以字母列出的试验代表对照实施例。
实施例1-用作CMP抛光试剂的亚胺衍生物
使用表1中所列的亚胺衍生物作为含氮抛光试剂用于CMP。在表头“R1”和“R2”中列出的结构对应于结构(I)中的取代基:
表1
无研磨剂抛光流体中的亚胺衍生化合物
*R21=-C(CH3)2-CH2-
R22=-CH2-C(CH3)2-
对于如实施例1和表1所述的亚胺衍生化合物,当其不含吸电子取代基而包含至少一个给电子取代基时,该化合物可提供良好的TaN去除速率和良好的去除选择性。因此,试验1-6的化合物包含给电子取代基,例如-NH2;-NH-C6H5;或-N(CH3)2。这些抛光试剂可提供至少400/min的无研磨剂TaN去除,和至少150的相对于电介质的去除选择性(TaN去除速率/TEOS的去除速率),和至少5的相对于金属的去除选择性(TaN去除速率/Cu的去除速率)。优选的试验1-4的亚胺衍生化合物只包含给电子取代基或者该取代基为氢。这些抛光试剂可提供至少1000/min的无研磨剂TaN去除,以及至少1000的相对于电介质的去除选择性(试验3),和至少10的相对于金属的去除选择性(试验2)。与此相反,试验A-G的化合物包含至少一个吸电子取代基如-OCH3;-NH-NO2;-SO2H;-NH-(CH2)3-CH(NH2)-C(=O)OH;或-C(CH3)2-CH2-N=N-CH2-C(CH3)2-C(NH2)=NH。这些抛光试剂表现出较低的TaN去除速率和相对于电介质和金属的不良的选择性。
实施例2-用作CMP抛光试剂的肼衍射物
使用表2中列出的肼衍生化合物作为含氮抛光试剂用于CMP。表3中给出了抛光的结果。在表头“R3”到“R6”中列出的结构对应于结构(II)中的取代基:
R3R4N-NR5R6(II)
表2
无研磨剂抛光流体中的肼衍生化合物
添加剂 | R<sup>3</sup> | R<sup>4</sup> | R<sup>5</sup> | R<sup>6</sup> |
碳酰肼 | -H | -H | -H | -C(=O)-NH-NH<sub>2</sub> |
乙酰肼 | -H | -H | -H | -C(=O)-CH<sub>3</sub> |
盐酸氨基脲 | -H | -H | -H | -C(=O)-NH<sub>2</sub>{·HCl} |
甲酰肼 | -H | -H | -H | -C(=O)H |
1,2-二甲酰肼 | -H | -C(=O)H | -H | -C(=O)H |
羧酸甲基肼 | -H | -CH<sub>3</sub> | -H | -C(=O)OH |
草酰二肼 | -H | -H | -H | -(C(=O))<sub>2</sub>-NH-NH<sub>2</sub> |
丙酮吖嗪 | - | =C(CH<sub>3</sub>)<sub>2</sub> | - | =C(CH<sub>3</sub>)<sub>2</sub> |
表3
无研磨剂抛光流体中的肼衍生化合物
对于实施例2和表2-3中所描述的肼衍生化合物,当其包含肼官能团(>N-NH2)和至多一个吸电子取代基时,该化合物可提供良好的TaN去除速率和良好的去除选择性。当R3和R4两者均为氢时,可以在这些实例中提供肼官能团。因此试验8-14的化合物包含肼官能团和至多一个吸电子取代基。即使存在吸电子基例如非酰胺羰基时,这些抛光试剂也可以提供良好的TaN去除速率。这些抛光试剂可提供至少1000/min的无研磨剂TaN去除,和至少500的相对于电介质的去除选择性(试验13),和至少10的相对于金属的去除选择性(试验12)。与此相反,试验H-M的化合物或者不包含肼官能团(试验H-I和M)或者包含一个以上的吸电子取代基(即两个非酰胺羰基;试验J-L)。这些抛光试剂表现出较低的TaN去除速率和不良的相对于电介质和金属的去除选择性。
根据这些实施例的结果,如表1-3中所述,使用含有含氮抛光试剂的无研磨剂抛光流体可以获得高的TaN阻挡层薄膜去除速率。特别地,某些类型亚胺衍生化合物和肼衍生化合物可以提供良好的TaN去除速率。对于试验1-6(表1)和试验7-14(表3)观察到至少400埃每分钟(/min)的良好的TaN去除速率。优选的含氮抛光试剂提供了至少1000/min的TaN去除速率(试验1-4和7-14)。
表1-3中所示的结果提供的数据表明,当使用含有含氮抛光试剂的无研磨剂抛光流体时,可以产生足够的阻挡层薄膜(TaN)的去除以及相对于金属薄膜(Cu)和电介质层(TEOS)的良好去除选择性。如前面所述,含有含氮抛光试剂的该CMP抛光流体可以提供高的去除速率,低的腐蚀速率和低的凹陷速率等优点。特别地,亚胺衍生物和肼衍生物促进了含钽阻挡层的去除。此外,该流体减少的或者无研磨剂颗粒的含量可减少电介质的腐蚀和互连金属的凹陷。
Claims (8)
1.用于抛光半导体衬底的含钽阻挡层材料的抛光流体,所述半导体具有铜或铜合金互连,该流体包含:
0.1-10wt%具有至少两个氮原子的含氮化合物,该含氮化合物是选自下述化合物中的至少一种:
胍和甲脒和如下式的肼化合物:R3R4N-NR5R6 (II)
其中R3,R4,R5和R6独立地选自下列的取代基:-H,烃基,氨基,亚氨基,偶氮基,氰基和其中的R7选自烃基的-OR7,并且该含氮化合物不含吸电子取代基;
0.0025-2wt%苯并三唑;且
所述抛光流体的pH为8-11,且不包含研磨剂颗粒,该抛光流体能够无需研磨剂的从半导体衬底的表面去除含钽的阻挡层材料。
2.权利要求1的抛光流体,其中该含氮化合物是选自胍或甲脒的至少一种。
3.权利要求1的抛光流体,其中该含氮化合物选自肼化合物。
4.用于抛光半导体衬底的含钽阻挡层材料的抛光流体,所述半导体具有铜或铜合金互连,该流体包含:
0.0025至2wt%用于减少铜或铜合金互连去除的苯并三唑;
0至25wt%的氧化剂;
0至15wt%的配位剂和
0.05至25wt%的含氮化合物,该含氮化合物具有至少两个氮原子且选自下述化合物中的至少一种:
1,3-二苯胍,盐酸胍,四甲基胍,乙酸甲脒,和盐酸乙脒和肼化合物
所述肼化合物是选自碳酰肼、乙酰肼、盐酸氨基脲和甲酰肼中的至少一种,
该含氮化合物不含吸电子取代基;该抛光流体的pH为8-11,且不包含研磨剂颗粒,所述抛光流体能够无需研磨剂的从半导体衬底的表面去除含钽的阻挡层材料。
5.权利要求4的抛光流体,其中该含氮化合物选自1,3-二苯胍,盐酸胍,四甲基胍,乙酸甲脒,和盐酸乙脒。
6.权利要求4的抛光流体,其中该含氮化合物是选自碳酰肼,乙酰肼,盐酸氨基脲,和甲酰肼中的至少一种。
7.用于抛光半导体衬底的方法,该半导体衬底具有铜或铜合金互连层和与该铜或铜合金互连层相邻的含钽阻挡层,该方法包括:
使用抛光流体阻挡层以便去除含钽阻挡层的至少一部分,该抛光流体不含研磨剂并且包含0.1-10重量%的含氮化合物,该含氮化合物具有至少两个氮原子且是选自下述化合物的至少一种:
胍和甲脒和如下式的肼化合物:R3R4N-NR5R6 (II)
其中R3,R4,R5和R6独立地是选自下列的取代基:-H,烃基,氨基,亚氨基,偶氮基,氰基和其中的R7选自烃基的-OR7,并且该含氮化合物不含吸电子取代基;该抛光流体能够无需研磨剂的从半导体衬底的表面去除含钽的阻挡层材料;0.0025-2重量%用于减少铜或铜合金互连去除的苯并三唑;且抛光流体的pH为8-11,且不包含研磨剂颗粒,所述抛光流体能够无需研磨剂的从半导体衬底的表面去除含钽的阻挡层材料。
8.权利要求7的方法,其中该含钽阻挡层选自钽或氮化钽且该抛光去除含钽阻挡层的至少一部分。
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- 2004-09-14 EP EP04255561A patent/EP1520894B1/en active Active
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2006
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Also Published As
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KR101234331B1 (ko) | 2013-02-18 |
EP1520894B1 (en) | 2011-06-08 |
EP1520894A1 (en) | 2005-04-06 |
TWI365908B (en) | 2012-06-11 |
KR20120019496A (ko) | 2012-03-06 |
CN1616571A (zh) | 2005-05-18 |
KR20050030582A (ko) | 2005-03-30 |
US7767581B2 (en) | 2010-08-03 |
US20060207635A1 (en) | 2006-09-21 |
TW200517482A (en) | 2005-06-01 |
JP2005136388A (ja) | 2005-05-26 |
US7241725B2 (en) | 2007-07-10 |
US20050070211A1 (en) | 2005-03-31 |
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