TWI593789B - Polishing composition and polishing method - Google Patents
Polishing composition and polishing method Download PDFInfo
- Publication number
- TWI593789B TWI593789B TW099142610A TW99142610A TWI593789B TW I593789 B TWI593789 B TW I593789B TW 099142610 A TW099142610 A TW 099142610A TW 99142610 A TW99142610 A TW 99142610A TW I593789 B TWI593789 B TW I593789B
- Authority
- TW
- Taiwan
- Prior art keywords
- polishing
- acid
- polishing composition
- polished
- indole
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims description 206
- 239000000203 mixture Substances 0.000 title claims description 106
- 238000000034 method Methods 0.000 title claims description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 30
- 239000004020 conductor Substances 0.000 claims description 27
- 239000000470 constituent Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 23
- 239000007800 oxidant agent Substances 0.000 claims description 18
- 229920000768 polyamine Polymers 0.000 claims description 9
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- -1 polyoxyethylene lauryl ether ammonium sulfate Polymers 0.000 description 50
- 150000001875 compounds Chemical class 0.000 description 33
- 230000001681 protective effect Effects 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 20
- 229910052684 Cerium Inorganic materials 0.000 description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 16
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 230000004888 barrier function Effects 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 12
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- 150000002391 heterocyclic compounds Chemical class 0.000 description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 8
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- 239000000126 substance Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
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- 229910052707 ruthenium Inorganic materials 0.000 description 6
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 6
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- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 description 4
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- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
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- 238000001179 sorption measurement Methods 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
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- 108010077895 Sarcosine Proteins 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 3
- UODZHRGDSPLRMD-UHFFFAOYSA-N sym-homospermidine Chemical compound NCCCCNCCCCN UODZHRGDSPLRMD-UHFFFAOYSA-N 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- ZUHDIDYOAZNPBV-UHFFFAOYSA-N 2-[2-hydroxyethyl-[(4-methylbenzotriazol-1-yl)methyl]amino]ethanol Chemical compound CC1=CC=CC2=C1N=NN2CN(CCO)CCO ZUHDIDYOAZNPBV-UHFFFAOYSA-N 0.000 description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 2
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- PWSZRRFDVPMZGM-UHFFFAOYSA-N 5-phenyl-1h-pyrazol-3-amine Chemical compound N1N=C(N)C=C1C1=CC=CC=C1 PWSZRRFDVPMZGM-UHFFFAOYSA-N 0.000 description 2
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- QMPFMODFBNEYJH-UHFFFAOYSA-N methyl 1h-1,2,4-triazole-5-carboxylate Chemical compound COC(=O)C1=NC=NN1 QMPFMODFBNEYJH-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229960001404 quinidine Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229940034208 thyroxine Drugs 0.000 description 1
- XUIIKFGFIJCVMT-UHFFFAOYSA-N thyroxine-binding globulin Natural products IC1=CC(CC([NH3+])C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 XUIIKFGFIJCVMT-UHFFFAOYSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229960004799 tryptophan Drugs 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 150000003668 tyrosines Chemical class 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/08—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for polishing surfaces, e.g. smoothing a surface by making use of liquid-borne abrasives
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/06—Other polishing compositions
- C09G1/14—Other polishing compositions based on non-waxy substances
- C09G1/16—Other polishing compositions based on non-waxy substances on natural or synthetic resins
-
- 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
- C09G1/06—Other polishing compositions
- C09G1/14—Other polishing compositions based on non-waxy substances
- C09G1/18—Other polishing compositions based on non-waxy substances on other substances
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明係有關一種可適合使用為形成半導體裝置之配線時的研磨處理之研磨用組成物及使用其之研磨方法。
形成半導體裝置之配線時，係先在具有凹溝(trench)之絕緣體上順序形成阻障層及導體層。然後，藉由化學機械研磨處理，除去至少位於凹溝外之導體層的部分(導體層之外側部分)及位於凹溝外之阻障層部分(阻障層之外側部分)。為除去該至少導體層之外側部分及阻障層之外側部分時的研磨處理，通常分為第1研磨步驟與第2研磨步驟進行。第1研磨步驟係使阻障層之上面露出，除去部分導體層之外側部分。然後，第2研磨步驟係使絕緣層露出，同時得到平坦的表面，除去至少導體層之外側部分的殘份及阻障層之外側部分。
為形成該半導體裝置之配線時的研磨處理，特別是第2研磨步驟之研磨處理中，一般使用含有酸等之研磨促進劑及氧化劑，另視其所需含有研磨砥粒之研磨用組成物。另外，亦提案使用可改善研磨處理後之研磨對象物的平坦性，尚添加水溶性高分子之研磨用組成物。例如，於專利文獻1中揭示，使用含有聚氧化乙烯月桂醚硫酸銨等之陰離子界面活性劑、苯并三唑等之保護膜形成劑及聚氧化乙烯烷醚等之非離子界面活性劑的研磨用組成物。於專利文
獻2中揭示，使用含有環氧鹵丙烷改性聚醯胺之研磨用組成物。而且，於專利文獻3中揭示，含有具藉由羧酸所修飾的胺基之化學修飾明膠的研磨用組成物。
此處，藉由化學機械研磨處理形成半導體裝置之配線時，特別是導體層由銅或銅合金所成時，在所形成的配線側面上產生不適合的凹陷情形。該配線側面之凹陷，係在位於與絕緣體層之邊界附近的導體層之部分表面於研磨處理時產生腐蝕的主要原因。即使使用上述習知之研磨用組成物，仍不易防止該配線側面產生凹陷情形。
[專利文獻1]日本特開2008-41781號公報
[專利文獻2]日本特開2002-110595號公報
[專利文獻3]日本特開2008-244316號公報
因此，本發明之目的係提供一種可更適合為形成半導體裝置之配線時的研磨處理之研磨用組成物及使用其之研磨方法。
為達成上述目的時，本發明之一實施形態係提供一種含有研磨促進劑與含有來自具胍構造之聚合性化合物的構成單位之水溶性聚合物與氧化劑的研磨用組成物。
具有胍構造之聚合性化合物，以下述一般式(1)或(2)所示之化合物較佳，以二氰二胺更佳。
於一般式(1)或(2)中，R1、R2、R3、R4、R5及R6係各獨立地表示氫原子、羥基、胺基、羧基、苯基、乙醯基，或碳數1~4之未經取代或經取代之烷基。
水溶性聚合物，亦可為含有來自二氰二胺的構成單位，與來自甲醛、二胺或聚胺之構成單位者。
本發明之另一形態，係提供一種使用上述形態之研磨用組成物，使具有由銅或銅合金所成的導體層之研磨對象物的表面進行研磨所成的研磨方法。
藉由本發明，提供一種可適合使用為形成半導體裝置之配線時的研磨處理之研磨用組成物及使用其之研磨方法。
於下述中，說明本發明之一實施形態。
本實施形態之研磨用組成物，係使研磨促進劑、特定的水溶性聚合物及氧化劑、較佳者與砥粒及保護膜形成劑
，與水混合予以調製。因此，研磨用組成物含有研磨促進劑、特定的水溶性聚合物及氧化劑，且較佳者尚含有砥粒及保護膜形成劑。
一般而言，於形成半導體裝置之配線時，係在具有凹溝之絕緣體層上順序形成阻障層及導體層予以進行。然後，藉由化學有機研磨處理除去至少位於凹溝外之導體層的部分(導體層之外側部分)及位於凹溝外之阻障層的部分(阻障層之外側部分)。為除去該至少導體層之外側部分及阻障層之外側部分時的研磨處理，通常分為第1研磨步驟及第2研磨步驟進行。第1研磨步驟，係使阻障層之上面露出，除去部分導體層之外側部分。然後，第2研磨步驟，係使絕緣體層露出，同時得到平坦的表面，至少除去導體層之外側部分的殘部及阻障層之外側部分。本實施形態之研磨用組成物，係主要使用於為形成該半導體裝置之配線時之研磨處理，特別是第2研磨步驟之研磨處理。換言之，研磨用組成物係主要使用於使具有導體層之研磨對象物表面進行研磨，形成半導體裝置之配線的用途。藉由化學機械研磨處理，形成半導體裝置之配線時，特別是導體層為由銅或銅合金所成者時，在所形成的配線側面上產生不適合的缺陷情形，本實施形態之研磨用組成物，可抑制該配線側面上產生凹陷的情形。而且，該研磨用組成物，於導體層由銅或銅合金所成時特別有用。
研磨用組成物中所含的研磨促進劑，係具有使研磨對象物之表面進行化學性蝕刻的作用，且可提高藉由研磨用組成物之研磨對象物體的研磨速度。
使用的研磨促進劑，例如可為無機酸、有機酸、胺基酸，及螯合劑中任何一種，較佳者為胺基酸或螯合劑。
無機酸之具體例，如硫酸、硝酸、硼酸、碳酸、次亞磷酸、亞磷酸，及磷酸。
有機酸之例，如甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊烷、正庚酸、2-甲基己酸、正辛酸、2-乙基己酸、苯甲酸、乙醇酸、水楊酸、丙三醇酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、苯二甲酸、蘋果酸、酒石酸、檸檬酸及乳酸，以及甲烷磺酸、乙烷磺酸，及羥乙磺酸等之有機硫酸。
可使用組合無機酸或有機酸、無機酸，或有機酸之銨鹽或鹼金屬鹽等之鹽取代無機酸或有機酸。組合弱酸與強鹼、強酸與弱鹼，或弱酸與弱鹼時，可期待PH值之緩衝作用。
胺基酸之具體例，如甘胺酸(glycine)、α-丙胺酸(alanine)、β-丙胺酸、N-甲基甘胺酸、N,N-二甲基甘胺酸、2-胺基丁酸、戊胺酸(norvaline)、擷胺酸(valine)、亮胺酸(leucine)、己胺酸(norleucine)、異亮胺酸苯基丙胺酸、脯胺酸(proline)、肌胺酸(sarcosine)、鳥胺酸(ornithin)、賴胺酸(lysine)、牛磺酸(taurine)、絲胺酸(serine)、蘇胺
酸(threonine)、高絲胺酸(homoserine)、酪胺酸(tyrosine)、N,N-雙(2-羥乙基)甘胺酸(bicine)、三羥甲基甘胺酸(tricine)、3,5-二碘化酪胺酸、β-(3,4-二羥基苯基)丙胺酸、甲狀腺素(thyroxine)、4-羥基-脯胺酸、半胱胺酸(cysteine)、蛋胺酸(methionine)、乙硫胺酸(ethionine)、羊毛硫胺酸(lanthionine)、磺基丙胺酸(cysteic acid)、天冬胺酸(aspartic acid)、谷胺酸(glutamic acid)、S-(羧基甲基)-胱硫醚(cystathionine)、4-胺基丁酸、天冬醯胺(asparagine)、谷胺醯胺(glutamine)、氮絲胺酸(azaserine)、精胺酸(arginine)、刀豆胺酸(canavanine)、瓜胺酸(citrullin)、δ-羥基-賴胺酸、肌酸(creatine)、組胺酸(histidine)、1-甲基-組胺酸、3-甲基-組胺酸，及色胺酸(tryptophane)。其中，甘胺酸、N-甲基甘胺酸、N,N-二甲基甘胺酸、α-丙胺酸、β-丙胺酸、N,N-雙(2-羥乙基)甘胺酸，及三羥甲基甘胺酸較佳，更佳者為甘胺酸。
螯合劑之具體例，如氰基三醋酸、二乙三胺五醋酸、乙二胺四醋酸、N,N,N-三亞甲基磷酸、乙二胺-N,N,N,’,N’-四亞甲基磺酸、反式環己烷二胺四醋酸、1,2-二胺基丙烷四醋酸、乙醇醚二胺四醋酸、乙二胺-o-羥基苯基醋酸、乙二胺二琥珀酸(SS體)、N-(2-羧根基乙基)-L-天冬胺酸、β-丙胺酸二醋酸、2-膦醯基丁烷-1,2,4-三羧酸、1-羥基亞乙基-1,1-二膦酸、N,N’-雙(2-羥基苯甲基)乙二胺-N,N’-二醋酸，及1,2-二羥基苯-4,6-二磺酸。
研磨用組成物中研磨促進劑之含量，以0.01g/L以上較
佳、更佳者為0.1g/L以上、最佳者為1g/L以上。伴隨研磨促進劑之含量增多，可更為提高藉由研磨用組成物之研磨對象物的研磨速度。
另外，研磨用組成物中研磨促進劑之含量，以50g/L以下較佳、更佳者為30g/L以下、最佳者為15g/L以下。伴隨研磨促進劑之含量減少，可減少藉由研磨促進劑引起研磨對象物表面過度蝕刻的情形。
研磨用組成物所含的水溶性聚合物，係藉由在研磨對象物之導體層表面上形成保護膜，具有可減少藉由研磨用組成物體之研磨處理所形成的配線側面產生凹陷的作用。
水溶性聚合物係使用包含來自具有胍構造之聚合性化合物的構成單位者。水溶性聚合物，除來自具有胍構造之聚合性化合物的構成單位外，尚含有來自其他聚合性化合物之構成單位。換言之，所使用的水溶性聚合物，係使具有胍構造之聚合性化合物均聚合、或與一種或複數種其他的聚合性化合物共聚合所得者。
包含來自具有胍構造之聚合性化合物的構成單位之水溶性聚合物，例如可使用於日本特開平4-45148號公報(申請人：三洋化成工業股份有限公司)、特開平6-172615號公報(申請人：三井東壓化學股份有限公司)，及特開2001-234155號公報(申請人：SENKA股份有限公司)中揭示，以習知的方法所合成者，亦可使用市售品。例如，
可使用SENKA股份有限公司製之UNISENCE KHP10P或UNISENCE KHF10P、日華化學股份有限公司製之NEOFIX RP70或NEOFIX FY及NIPPON CARBIDE INDUSTRIES股份有限公司製之NIKAFLOCK D-100。
包含來自胍構造之聚合性化合物的構成單位之水溶性聚合物，推測以本身具有的氮原子作為吸附側，吸附於研磨對象物之導體層表面上，形成保護膜，惟來自具有胍構造之聚合性化合物的構成單位，存在作為水溶性聚合物之吸附側的機能之氮原子的密度高的地方。因此，該水溶性聚合物與其他水溶性聚合物相比時，可藉由研磨對象物之導體層(亦包含部分位於與絕緣體層之邊界附近的導體層)表面，確實地形成保護膜。藉此，位於與絕緣體層之邊界附近的導體層之部分表面，於研磨處理時不易產生被腐蝕，結果可抑制配線側面產生凹陷的情形。
除來自具有胍構造之聚合性化合物的構成單位外，在水溶性聚合物中包含來自其他聚合性化合物之構成單位時，作為吸附側之機能的氮原子之密度高的地方，於水溶性聚合物之分子內適當地分散配置，結果，不易引起水溶性聚合物吸附於研磨用組成物中任意含有的砥粒之情形。此係就提高砥粒之分散性而言極為有利。
具有胍構造之聚合性化合物，以下述一般式(1)或(2)所示之化合物較佳，更佳者為二氰二胺。
於一般式(1)及(2)中，R1、R2、R3、R4、R5及R6係各獨立地表示氫原子、羥基、胺基、羧基、苯基、乙醯基，或碳數1~4之未經取代或經取代之烷基。碳數1~4之經取代的烷基之具體例，如甲基、乙基、丙基、異丙基，及第3-丁基。碳數1~4之經取代的烷基之具體例，如甲基、乙基、丙基、異丙基，及第3-丁基等之未經取代的烷基中至少一個氫原子以羥基、胺基、羧基等取代基所取代者，換言之，例如羥基甲基、羥基乙基、羥基丙基、胺基甲基、胺基乙基、羧基甲基、羧基乙基、2,3-二羥基丙基、2-羥基-3-胺基丙基，及3-羥基-2-胺基丙基。
水溶性聚合物之分子量，以500以上較佳，更佳者為1,000以上，最佳者為2,000以上。伴隨水溶性聚合物之分子量增多，可更為抑制藉由在使用研磨用組成物之研磨處理所形成的配線側面產生凹陷的情形。
另外，水溶性聚合物之分子量，以100,000以下較佳，更佳者為20,000以下，最佳者為10,000以下。伴隨水溶性聚合物之分子量減少，可更為提高研磨用組成物中任意含有的砥粒之分散性。
研磨用組成物中水溶性聚合物之含量，以視研磨用組
成物中所含的研磨促進劑之量或氧化劑之量而定予以適當設定為宜，一般而言，以0.001g/L以上較佳，更佳者為0.005g/L以上，最佳者為0.01g/L以上。伴隨水溶性聚合物之含量增多，可更為抑制藉由在使用研磨用組成物之研磨處理所形成的配線側面產生凹陷的情形。
研磨用組成物中水溶性聚合物之含量，以1g/L以下較佳，更佳者為0.5g/L以下，最佳者為0.2g/L以下。伴隨水溶性聚合物之含量減少，除可更為抑制研磨用組成物之材料成本外，可更為抑制使用研磨用組成物進行研磨後之研磨對象物表面上產生碟型凹陷(dishing)現象。而且，碟型凹陷係指部份原本不應被除去，位於凹溝中之導體層被研磨除去，導體層上面之水平降低，在研磨對象物表面上產生碟狀凹陷(dish)現象。
除來自二氰二胺等之具有胍構造的聚合性化合物之構成單位外，於水溶性聚合物中尚包含來自其他聚合性化合物之構成單位時，來自其他聚合性化合物之構成單位，以來自甲醛、二胺或聚胺之構成單位較佳。換言之，水溶性聚合物亦可為使胍構造之聚合性化合物，與至少甲醛、二胺或聚胺共聚合所得者。而且，UNISENCE KHP10P及NEOFIX RP70係含有來自二氰二胺之構成單位與來自聚胺之構成單位之水溶性聚合物，UNISENCE KHF10P、NEOFIX FY及NIKAFLOCK D-100係含有來自二氰二胺之構成單位與來自甲醛之構成單位的水溶性聚合物。
二胺之具體例，如乙二胺、三亞甲二胺、丙二胺、四
亞甲二胺、五亞甲二胺、六亞甲二胺、七亞甲二胺、對苯二胺、N-(2-羥基乙基)-1,2-乙二胺，及2-羥基-1,3-丙二胺。其中，以乙二胺、丙二胺、四亞甲二胺、五亞甲二胺、六亞甲二胺、七亞甲二胺，及對苯二胺較佳。
聚胺之具體例，如二乙三胺、三乙四胺、四乙五胺、五乙六胺、雙(3-胺基丙基)胺、雙(4-胺基丁基)胺、亞胺基雙丙胺、甲基雙(3-胺基丙基)胺、N,N’-雙(3-胺基丙基)-1,4-丁二胺、N-(3-胺基丙基)-1,4-丁二胺、N-(4-胺基丁基)-1,4-丁二胺等之聚伸烷基聚胺。其中，以二乙三胺、三乙四胺、四乙五胺、五乙六胺，及亞胺基雙丙胺較佳，更佳者為二乙三胺及三乙四胺。
使具有胍構造之聚合性化合物與其他聚合性化合物共聚合，製得水溶性聚合物時，相對於其他聚合性化合物之莫耳數而言，具有胍構造之聚合性化合物的莫耳數比例以1/50以上較佳、更佳者為1/20以上、最佳者為1/10以上。伴隨具有胍構造之聚合性化合物的比例增多，可更為抑制藉由在使用研磨用組成物之研磨處理所形成的配線側面產生凹陷的現象。
此外，相對於其他聚合性化合物之莫耳數而言，具有胍構造之聚合性化合物的莫耳數比例，以50/1以下較佳，更佳者為20/1以下，最佳者為10/1以下。伴隨具有胍構造之聚合性化合物的比例減少，可更為提高研磨用組成物中任意含有的砥粒之分散性。
研磨用組成物中所含的氧化劑，具有使研磨對象物之表面氧化的作用，且可提高藉由研磨用組成物之研磨對象物的研磨速度。
氧化劑例如可使用過氧化物。過氧化物之具體例，如過氧化氫、過醋酸、過碳酸鹽、過氧化尿素及過氯酸，及過硫酸鈉、過硫酸鉀、過硫酸銨等之過硫酸鹽。其中，以過氧化氫及過硫酸鹽較佳，更佳者為過氧化氫。
研磨用組成物中氧化物之含量，以0.1g/L以上較佳，更佳者為1g/L以上，最佳者為3g/L以上。伴隨氧化劑之含量增多，可更為提高藉由研磨用組成物之研磨對象物的研磨速度。
另外，研磨用組成物中氧化劑之含量，以200g/L以下較佳，更佳者為100g/L以下，最佳者為40g/L以下。伴隨氧化劑之含量減少，除可更為抑制研磨用組成物之材料成本外，且可減輕研磨使用後研磨用組成物之處理、即廢液處理之負荷。此外，亦可減少因氧化劑所引起的研磨對象表面之過剩氧化情形。
研磨用組成物中任意含有的砥粒，具有使研磨對象物體進行機械性研磨的作用，且可提高藉由研磨用組成物之研磨對象物的研磨速度。
所使用的砥粒，可為無機粒子、有機粒子，及有機無
機複合粒子中任何一種。無機粒子之具體例，如由二氧化矽、氧化鋁、氧化鈰、氧化鈦等之金屬氧化物所成的粒子，以及氮化矽粒子、碳化矽粒子，及氮化硼粒子。其中，以二氧化矽較佳，更佳者為膠體二氧化矽。有機粒子之具體例，如聚甲基丙烯酸甲酯(PMMA)粒子。
研磨用組成物中砥粒之含量，以0.005質量%以上較佳，更佳者為0.01質量%以上，最佳者為0.05質量%以上。伴隨砥粒之含量增多，可更為提高藉由研磨用組成物之研磨對象物的研磨速度。
另外，研磨用組成物中砥粒之含量，以5質量%以下較佳，更佳者為1質量%以下，最佳者為0.5質量%以下。伴隨砥粒之含量減少，除可更為抑制研磨用組成物之材料成本外，可更為抑制在使用研磨用組成物進行研磨後之研磨對象物表面上產生的碟型凹陷現象。
砥粒之平均一次粒徑，以5nm以上較佳，更佳者為7nm以上，最佳者為10nm以上。伴隨砥粒之平均一次粒徑增大，可更為提高藉由研磨用組成物之研磨對象物的研磨速度。
此外，砥粒之平均一次粒徑，以100nm以下較佳，更佳者為60nm以下，最佳者為40nm以下。伴隨砥粒之平均一次粒徑變小，可更為抑制在使用研磨用組成物進行研磨後之研磨對象物表面上產生的碟型凹陷現象。而且，砥粒之平均一次粒徑之值，例如以BET法所測定的砥粒之比表面積為基準算出。
於研磨用組成物中加入保護膜形成劑時，可更為抑制藉由使用研磨用組成物之研磨處理所形成的配線側面產生的凹陷現象。另外，可更為抑制在使用研磨用組成物進行研磨後之研磨對象物表面上產生的碟型凹陷現象。而且，可更為提高使用研磨用組成物進行研磨後之研磨對象物表面的平坦性。
所使用的保護膜形成劑，沒有特別的限制，較佳者為雜環式化合物或界面活性劑。雜環式化合物中雜環之環數，沒有特別的限制。而且，雜環式化合物可以為單環化合物，亦可為具有縮合環之多環化合物。
作為保護膜形成劑使用的雜環化合物之具體例，如吡咯、吡唑、咪唑、三唑、四唑、吡啶、吡嗪、噠嗪、4-氮茚(pyrindine)、吲哚嗪、吲哚、異吲哚、吲唑、卜啉、喹啶、喹啉、異喹啉、萘錠、酞嗪、喹喔啉、喹唑啉、噌啉、蝶啶、噻唑、異噻唑、噁唑、異噁唑、呋咱等之含氮雜環化合物。
吡唑之例，如包含1H-吡唑、4-硝基-3-吡唑羧酸、3,5-吡唑羧酸、3-胺基-5-苯基吡唑、5-胺基-3-苯基吡唑、3,4,5-三溴吡唑、3-胺基吡唑、3,5-二甲基吡唑、3,5-二甲基-1-羥基甲基吡唑、3-甲基吡唑、1-甲基吡唑、3-胺基-5-甲基吡唑、4-胺基-吡唑并[3,4-d]嘧啶、異嘌呤醇、4-氯-1-吡唑并[3,4-d]嘧啶、3,4-二羥基-6-甲基吡唑并-[3,4-b]吡
啶及6-甲基-1H-吡唑并[3,4-b]吡啶-3-胺。
咪唑之例，如包含咪唑、1-甲基咪唑、2-甲基咪唑、4-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-異丙基咪唑、苯并咪唑、5,6-二甲基苯并咪唑、2-胺基苯并咪唑、2-氯化苯并咪唑、2-甲基苯并咪唑、2-(1-羥基乙基)苯并咪唑、2-羥基苯并咪唑、2-苯基苯并咪唑、2,5-二甲基苯并咪唑、5-甲基苯并咪唑、5-硝基苯并咪唑，及1H-卜啉。
三唑之例，如包含1,2,3-三唑、1,2,4-三唑、1-甲基-1,2,4-三唑、甲基-1H-1,2,4-三唑-3-羧酸酯、1,2,4-三唑-3-羧酸、1,2,4-三唑-3-羧酸甲酯、1H-1,2,4-三唑-3-硫醇、3,5-二胺基-1H-1,2,4-三唑、3-胺基-1,2,4-三唑-5-硫醇、3-胺基-1H-1,2,4-三唑、3-胺基-5-苯甲基-4H-1,2,4-三唑、3-胺基-5-甲基-4H-1,2,4-三唑、3-硝基-1,2,4-三唑、3-溴-5-硝基-1,2,4-三唑、4-(1,2,4-三唑-1-基)苯酚、4-胺基-1,2,4-三唑、4-胺基-3,5-二丙基-4H-1,2,4-三唑、4-胺基-3,5-二甲基-4H-1,2,4-三唑、4-胺基-3,5-二庚基-4H-1,2,4-三唑、5-甲基-1,2,4-三唑-3,4-二胺、1H-苯并三唑、1-羥基苯并三唑、1-胺基苯并三唑、1-羧基苯并三唑、5-氯-1H-苯并三唑、5-硝基-1H-苯并三唑、5-羧基-1H-苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-(1,2’-二羧基乙基)苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑，及1-[N,N-雙(羥基乙基)胺基甲基]-4-甲
基苯并三唑。
四唑之例，如包含1H-四唑、5-甲基四唑、5-胺基四唑，及5-苯基四唑。
吲唑之例，如1H-吲唑、5-胺基-1H-吲唑、5-硝基-1H-吲唑、5-羥基-1H-吲唑、6-胺基-1H-吲唑、6-硝基-1H-吲唑、6-羥基-1H-吲唑，及3-羧基-5-甲基-1H-吲唑。
吲哚之例，如1H-吲哚、1-甲基-1H-吲哚、2-甲基-1H-吲哚、3-甲基-1H-吲哚、4-甲基-1H-吲哚、5-甲基-1H-吲哚、6-甲基-1H-吲哚、7-甲基-1H-吲哚、4-胺基-1H-吲哚、5-胺基-1H-吲哚、6-胺基-1H-吲哚、7-胺基-1H-吲哚、4-羥基-1H-吲哚、5-羥基-1H-吲哚、6-羥基-1H-吲哚、7-羥基-1H-吲哚、4-甲氧基-1H-吲哚、5-甲氧基-1H-吲哚、6-甲氧基-1H-吲哚、7-甲氧基-1H-吲哚、4-氯-1H-吲哚、5-氯-1H-吲哚、6-氯-1H-吲哚、7-氯-1H-吲哚、4-羧基-1H-吲哚、5-羧基-1H-吲哚、6-羧基-1H-吲哚、7-羧基-1H-吲哚、4-硝基-1H-吲哚、5-硝基-1H-吲哚、6-硝基-1H-吲哚、7-硝基-1H-吲哚、4-硝基二甲苯-1H-吲哚、5-硝基二甲苯-1H-吲哚、6-硝基二甲苯-1H-吲哚、7-硝基二甲苯-1H-吲哚、2,5-二甲基-1H-吲哚、1,2-二甲基-1H-吲哚、1,3-二甲基-1H-吲哚、2,3-二甲基-1H-吲哚、5-胺基-2,3-二甲基-1H-吲哚、7-乙基-1H-吲哚、5-(胺基甲基)吲哚、2-甲基-5-胺基-1H-吲哚、3-羥基甲基-1H-吲哚、6-異丙基-1H-吲哚，及5-氯-2-甲基-1H-吲哚。
其中，較佳的雜環化合物為具有三唑骨架之化合物，
即以1H-苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-4-甲基苯并三唑、1,2,3-三唑，及1,2,4-三唑更佳。此等之雜環化合物，為提高對研磨對象物表面之化學或物理性吸附力時，在研磨對象物表面上形成更為堅固的保護膜。此係就提高使用研磨用組成物進行研磨後之研磨對象物表面的平坦性而言極為有利。
作為保護膜形成劑所使用的界面活性劑，可為陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑，及非離子性界面活性劑中任何一種皆可。
陰離子界面活性劑之例，如包含聚氧化乙烯烷醚醋酸、聚氧化乙烯烷基硫酸酯、烷基硫酸酯、聚氧化乙烯烷基硫酸、烷基硫酸、烷基苯磺酸、烷基磷酸酯、聚氧化乙烯烷基磷酸酯、聚氧化乙烯磺基琥珀酸、烷基磺基琥珀酸、烷基萘磺酸、烷基二苯醚二磺酸，及此等之鹽。
陽離子性界面活性劑之例，如包含烷基三甲銨鹽、烷基二甲銨鹽、烷基苯甲基二甲銨鹽，及烷胺鹽。
兩性界面活性劑之例，如包含烷基甜菜鹼及氧化烷胺。
非離子性界面活性劑之例，如聚氧化乙烯烷醚、聚氧化亞烷基烷醚、山梨糖醇酐脂肪酸酯、丙三醇脂肪酸酯、聚氧化乙烯脂肪酸酯、聚氧化乙烯烷胺，及烷基鏈烷醇醯胺。
其中，較佳的界面活性劑有聚氧化乙烯烷醚醋酸、聚氧化乙烯烷醚硫酸鹽、烷醚硫酸鹽、烷基苯磺酸鹽，及聚氧化乙烯烷醚。此等之界面活性劑，為提高對研磨對象物表面之化學或物理性吸附力時，在研磨對象物表面上形成更為堅固的保護膜。此係就提高使用研磨用組成物進行研磨後之研磨對象物表面的平坦性而言極為有利。
研磨用組成物中保護膜形成劑之含量，以0.001g/L以上較佳，更佳者為0.005g/L以上，最佳者為0.01g/L以上。伴隨保護膜形成劑之含量增多，可更為提高使用研磨用組成物進行研磨後之研磨對象物表面的平坦性。
研磨用組成物中保護膜形成劑之含量，以10g/L以下較佳，更佳者為5g/L以下，最佳者為1g/L以下。伴隨保護膜形成劑之含量減少，可更為提高藉由研磨用組成物之研磨對象物的研磨速度。
研磨用組成物之pH值，以3以上較佳，更佳者為5以上。伴隨研磨用組成物之pH值增大，可減少因研磨用組成物而引起研磨對象物表面之過剩蝕刻現象。
研磨用組成物之pH值，以9以下較佳，更佳者為8以下。伴隨研磨用組成物之pH值減小，可更為抑制藉由使用研磨用組成物之研磨處理所形成的配線側面產生的凹陷現象。
為得企求的pH值時，亦可使用任意的鹼、酸及緩衝劑
。
藉由本實施形態，可得下述之優點。
本實施形態之研磨用組成物，含有包含來自具胍構造之聚合性化合物的構成單位之水溶性聚合物。因此，藉由該水溶性聚合物之作用，可抑制藉由使用研磨用組成物之研磨處理所形成的配線側面產生的凹陷現象。因此，本實施形態之研磨用組成物，可適合使用於為形成半導體裝置之配線時之研磨處理。
前述實施形態亦可改為如下述所示。
‧前述實施形態之研磨用組成物，亦可含有二種以上之研磨促進劑。
‧前述實施形態之研磨用組成物，亦可含有二種以上之水溶性聚合物。
此時，有關部份的水溶性聚合物，不一定必須為包含有來自具有胍構造之聚合性化合物的構成單位。該水溶性聚合物之具體例，如褐藻酸、果膠酸、羧基甲基纖維素、卡特蘭多醣、聚三葡萄糖等之多糖類、聚羧酸及其鹽、聚丙烯醯胺、聚乙烯醇、聚乙烯基吡咯烷酮、聚丙烯醛等之乙烯基系聚合物、聚丙三醇及聚丙三醇酯。在研磨用組成物中添加不含來自具有胍構造之聚合性化合物的構造單位之水溶性聚合物時，就除該水溶性聚合物吸附於砥粒表面或研磨對象物表面上，藉由研磨用組成物可控制研磨對象物之研磨速度外，且就可藉由水溶性聚合物體，使研磨中產生的不溶性成分在研磨用組成物中安定化而言，極為有
利。
‧前述實施形態之研磨用組成物，亦可含有二種以上之氧化劑。
‧前述實施形態之研磨用組成物，亦可含有二種以上之砥粒。
‧前述實施形態之研磨用組成物，亦可含有二種以上之保護膜形成劑。
此時，例如可使用二種以上之雜環式化合物，亦可使用二種以上之界面活性劑。另外，亦可組合雜環式化合物與界面活性劑使用。組合雜環式化合物與界面活性劑使用時、即研磨用組成物含有雜環式化合物及界面活性劑時，可容易使提高藉由研磨用組成物之研磨對象物的研磨速度，與提高使用研磨用組成物進行研磨後之研磨對象物表面的平坦性兩者併立。
‧前述實施形態之研磨用組成物，視其所需尚可含有如防腐蝕劑或防霉劑之習知添加劑。防腐蝕劑及防霉劑之具體例，如2-甲基-4-異噻唑啉-3-酮、5-氯-2-甲基-4-異噻唑啉-3-酮等之異噻唑啉系防腐蝕劑、對氧化苯甲酸酯類，及苯氧基乙醇。
‧前述實施形態之研磨用組成物，可為一液型，亦可為以二液型為始的多液型。
‧前述實施形態之研磨用組成物，藉由使研磨用組成物之原液使用水等之稀釋液稀釋成例如10倍以上，予以調製。
‧前述實施形態之研磨用組成物，亦可被使用於除為形成半導體裝置之配線時的研磨處理以外之用途。
其次，說明本發明之實施例及比較例。
將研磨促進劑、水溶性聚合物或取代它之化合物、氧化劑、砥粒，及保護膜形成劑與水混合，調製實施例1~17及比較例4~22之研磨用組成物。將研磨促進劑、氧化劑、砥粒，及保護膜形成劑與水混合，調製比較例1~3之研磨用組成物。實施例1~17及比較例1~22之研磨用組成物中之水溶性聚合物或取代它之化合物的詳述說明，如表1及表2所示。而且，於表1及表2中雖沒有表示，惟實施例1~17及比較例1~22之研磨用組成物，皆含有10g/L作為研磨促進劑之甘胺酸、15g/L作為氧化劑之過氧化氫、0.1質量%作為砥粒之平均一次粒徑為30nm之膠體二氧化矽。另外，實施例1~17及比較例1~22之研磨用組成物，皆含有0.08g/L之作為保護膜形成劑之1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑及1-[N,N-雙(羥基乙基)胺基甲基]-4-甲基苯并三唑之混合物、0.1g/L之月桂醚硫酸銨，與0.5g/L之聚氧化乙烯烷醚，於其中尚可追加任意量的保護膜形成劑。部分研磨用組成物中所含追加的保護膜形成劑之詳述說明，如表1及表2所示。
使用各例之研磨用組成物，使銅圖案晶圓(ATDF754光罩、研磨處理前之銅膜厚700nm、凹溝深度300nm)之表面，以表3記載的第1之研磨條件進行研磨至銅膜厚為250nm為止。然後，使研磨後之銅圖案晶圓之表面使用相同的研磨用組成物，以表4記載的第2研磨條件進行研磨至阻礙膜露出為止。使進行該2個階段後之銅圖案晶圓表面，使用Review SEM(Hitachi Hitechnology股份有限公司製之RS-4000)進行觀察，於0.18μm寬度之配線與0.18μm寬度之絕緣膜相互並列的範圍及100μm寬度之配線與100μm寬度之絕緣膜相互並列的範圍中，確認是否有配線側面之凹陷情形。因此，於任何範圍內確認沒有配線側面之凹陷情形者為◎(優)，於任何範圍內僅確認寬度未達5nm之配線側面的凹陷者為○(佳)，於兩側範圍內確認有寬度未達5nm之配線側面的凹陷者為□(可)，於至少一側之範圍內確認有寬度5nm以上、未達20nm之配線側面的凹陷者為△(稍微不佳)，於至少一側之範圍內確認有寬度20nm以上之配線側面的凹陷者為×(不佳)。該評估結果如表5及表6之“配線側面之凹陷”欄所示。
使用各例之研磨用組成物，使銅殼晶圓之表面以表3記載之第1研磨條件及表4記載之第2研磨條件進行研磨60秒時之第1條件及第2條件的各研磨速度，如表5及表6之“
研磨速度”欄所示。研磨速度之值係藉由日立國際電氣股份有限公司製之薄片電阻測定器“VR-120SD/8”所測定的研磨前後之銅殼晶圓之厚度差除以研磨時間求取。
使用在60℃下保管1周後、回復至室溫的各例之研磨用組成物，以與上述相同的方法進行評估配線側面之凹陷及測定研磨速度，與保管前之研磨用組成物之各評估與測定相比。另外，有關評估砥粒之分散性，相同地在60℃下保管1周後，回復至室溫之各例的研磨用組成物使用島津製作所股份有限公司製之分光光度計“UV-2450”，測定190nm~900nm之波長範圍之透過率，與保管前之研磨用組成物相比。然後，配線側面之凹陷的評估結果、研磨速度之測定結果及砥粒之分散性的評估結果，保管前後皆沒有差別時為◎(優)，有關配線側面之凹陷的評估結果及砥粒之分散性的評估結果，保管前後幾乎沒有差別，惟保管後研磨速度之值僅降低為5%以上、未達10%者為○(佳)，有關配線側面之凹陷的評估結果及砥粒之分散性的評估結果，保管前後幾乎沒有差別，惟保管後配線側面之凹陷的評估結果降低一階者為□(可)，保管後砥粒之分散性的評估結果有惡化情形者為△(稍微不佳)，保管後研磨速度之值降低10%以上或配線側面之凹陷的評估結果降低二階以上者為×(不佳)。該評估結果如表5及表6之“保存安定性”欄所示。
使用各例之研磨用組成物，使銅圖案晶圓(ATDF754光罩、研磨處理前之銅膜厚700nm、凹溝深度300nm)之表面，以表3記載的第1之研磨條件進行研磨至銅膜厚為250nm為止。然後，使研磨後之銅圖案晶圓之表面使用相同的研磨用組成物，以表4記載的第2研磨條件進行研磨至阻礙膜露出為止。使用SII‧Nanotechnology股份有限公司製之掃描型探針顯微鏡“S-image”測定進行該2階段研磨處理後之銅圖案晶圓的100μm寬度之孤立配線部中央附近的表面粗糙度Ra。該表面粗糙度Ra之測定，使用Si探針以DFM型進行，於1μm四方範圍內縱橫各256點、0.5Hz之掃描速度進行。所測定的Ra值未達0.5nm時為○(佳)，0.5nm以上、未達1.0nm時為△(稍微不佳)，1.0nm以上時為×(不佳)。該評估結果如表5及表6之“表面粗糙度”欄所示。
使用各例之研磨用組成物，使銅圖案晶圓(ATDF754光罩、研磨處理前之銅膜厚700nm、凹溝深度300nm)之表面，以表3記載的第1之研磨條件進行研磨至銅膜厚為250nm為止。然後，使研磨後之銅圖案晶圓之表面使用相同的研磨用組成物，以表4記載的第2研磨條件進行研磨至阻礙膜露出為止。於進行該2階段研磨處理後之銅圖案晶
圓的9μm寬度之配線與1μm寬度之絕緣膜相互並列的第1範圍及5μm寬度之配線與1μm寬度之絕緣膜相互並列的第2範圍內，使用Hitachi Kenki Fine Tech股份有限公司製之Wide Area AFM“WA-1300”，測定碟型凹陷量(碟型凹陷深度)。該測定之結果如表5及表6之“碟型凹陷”欄所示。
Claims (2)
- 一種研磨方法，其特徵為使用含有下述成分的研磨用組成物：研磨促進劑、與包含來自二氰二胺的構成單位與來自甲醛、二胺或聚胺的構成單位之水溶性聚合物、與氧化劑、與膠體二氧化矽之砥粒，研磨具有由銅或銅合金所構成的導體層之研磨對象物的表面。
- 一種抑制配線側面產生凹陷之研磨方法，其特徵為使用含有下述成分的研磨用組成物：研磨促進劑、與包含來自二氰二胺的構成單位與來自甲醛、二胺或聚胺的構成單位之水溶性聚合物、與氧化劑、與膠體二氧化矽之砥粒，研磨具有由銅或銅合金所構成的導體層之研磨對象物的表面。
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| US9640407B2 (en) * | 2011-06-14 | 2017-05-02 | Fujimi Incorporated | Polishing composition |
| WO2013077354A1 (ja) * | 2011-11-22 | 2013-05-30 | 国立大学法人東京大学 | セルロースナノファイバー分散液とその製造方法、セルロースナノファイバー修飾体、セルロースナノファイバー複合体 |
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2011
- 2011-02-18 CN CN201110041743.XA patent/CN102212315B/zh active Active
- 2011-03-08 KR KR1020110020179A patent/KR20110113131A/ko active IP Right Grant
- 2011-03-30 US US13/075,791 patent/US20110250754A1/en not_active Abandoned
- 2011-04-05 EP EP11161123.2A patent/EP2374852B1/en active Active
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2016
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201137097A (en) | 2011-11-01 |
| EP2374852A1 (en) | 2011-10-12 |
| KR20110113131A (ko) | 2011-10-14 |
| CN102212315A (zh) | 2011-10-12 |
| JP2011222716A (ja) | 2011-11-04 |
| CN102212315B (zh) | 2015-05-13 |
| US20160136784A1 (en) | 2016-05-19 |
| JP5774283B2 (ja) | 2015-09-09 |
| EP2374852B1 (en) | 2017-04-05 |
| US20110250754A1 (en) | 2011-10-13 |
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