TW543123B - Method of forming copper oxide film, method of etching copper film, and method of fabricating semiconductor device - Google Patents
Method of forming copper oxide film, method of etching copper film, and method of fabricating semiconductor device Download PDFInfo
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- TW543123B TW543123B TW089124469A TW89124469A TW543123B TW 543123 B TW543123 B TW 543123B TW 089124469 A TW089124469 A TW 089124469A TW 89124469 A TW89124469 A TW 89124469A TW 543123 B TW543123 B TW 543123B
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- Prior art keywords
- copper
- film
- oxide film
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 182
- 239000010949 copper Substances 0.000 title claims abstract description 182
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000005530 etching Methods 0.000 title claims abstract description 51
- 239000004065 semiconductor Substances 0.000 title claims abstract description 43
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 29
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 74
- 239000002184 metal Substances 0.000 claims abstract description 74
- 230000004888 barrier function Effects 0.000 claims abstract description 62
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 18
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 6
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims 4
- 238000007493 shaping process Methods 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 15
- 238000009413 insulation Methods 0.000 abstract description 14
- 230000001590 oxidative effect Effects 0.000 abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- 239000000126 substance Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 8
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Chemical compound ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910017974 NH40H Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
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- 229910052709 silver Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000014676 Phragmites communis Nutrition 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
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- 230000002411 adverse Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- -1 argon peroxide Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229960002050 hydrofluoric acid Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
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- 239000002689 soil Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- 238000001039 wet etching Methods 0.000 description 2
- HSINOMROUCMIEA-FGVHQWLLSA-N (2s,4r)-4-[(3r,5s,6r,7r,8s,9s,10s,13r,14s,17r)-6-ethyl-3,7-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]-2-methylpentanoic acid Chemical compound C([C@@]12C)C[C@@H](O)C[C@H]1[C@@H](CC)[C@@H](O)[C@@H]1[C@@H]2CC[C@]2(C)[C@@H]([C@H](C)C[C@H](C)C(O)=O)CC[C@H]21 HSINOMROUCMIEA-FGVHQWLLSA-N 0.000 description 1
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 206010011878 Deafness Diseases 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
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- 206010037180 Psychiatric symptoms Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- CNQCVBJFEGMYDW-UHFFFAOYSA-N lawrencium atom Chemical compound [Lr] CNQCVBJFEGMYDW-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
- H01L21/76849—Barrier, adhesion or liner layers formed in openings in a dielectric the layer being positioned on top of the main fill metal
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/63—Treatment of copper or alloys based thereon
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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
- H01L21/02041—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
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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
- H01L21/02041—Cleaning
- H01L21/02082—Cleaning product to be cleaned
- H01L21/02087—Cleaning of wafer edges
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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
- H01L21/02041—Cleaning
- H01L21/02082—Cleaning product to be cleaned
- H01L21/0209—Cleaning of wafer backside
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76865—Selective removal of parts of the layer
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76883—Post-treatment or after-treatment of the conductive material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Description
五、發明說明(1) 【發明之技術領域】 置ίΐ明是半導體積體電路之半導體裝置及有關半導體壯 置用之銅膜加工及其配線構造之製造方法¥體衣 【先前技術】 分:ϊί導ΐ積體電路之半導體裝置用銅或以銅為主要成 為j防止因此產生之錯誤動作, 如圖UU)所示屬在包/=^以隔絕絕緣層。 在絕緣膜上之配缘、、|、/基板上形成之配線通常是埋 體電路等之半導體是半導體基板之側面圖。積 形成碎氧化膜之Γ 3疋在以矽做成的半導體基板1 〇 〇上 在此配線溝之側==1 ’在其表面嫩 或以銅為主要成分二或埋壁金屬m ’銅膜1〇3 如此以往配線部分 〆、 至層間絕緣膜,對在半。=有障壁金屬之上方擴散 有不良影響。又因為=體基板100上形成之半導體元件 103表面以CMP法平±ti層間絕緣膜101及埋入其中之銅膜 無法辨識之圖形。—所以在刻版印.刷時會產生圖形蝕刻 針對此問題以餘列 去,使其如圖13(Μ Λ 將配線部分即銅膜1〇3上方除 使圖形對合。 斤不較層間絕緣膜101表面低。如此可 又如圖13(c)所示右盆 覆蓋層,如此可以阶上方覆蓋—層障壁金屬104或其他 止銅從上部擴散。若覆蓋層用導電材 543123 五、發明說明(2) 一 料則上層之配線和其穿孔配線(接觸配線)形成時因銅不會 直接暴露在蝕刻之環境中,故可降低發生腐蝕或因蝕刻而 斷線之危險。 【發明所欲解決之課題】 、如前所述以往形成配線溝構造的方法有溼式蝕刻法和乾 式餘刻法。乾式法又分成非等方向蝕刻之RIE (Reactive Ion Etching)法及等方向蝕刻之CDe (Chemical Dry
Etching j法。用此方法雖可以進行銅蝕刻但對地球的環境 有不良影響。如在乾式法中使用CF系的氣體。溼式法要除
去在蝕刻後堆積的副產品,相對的溼式處理在工程上及 本上有較多的問題。
f此將重點放在溼式蝕刻。銅幾乎不溶於鹽酸、氟酸 稀1酸、醋酸、氫氰酸等氧化力較弱的酸但會被具氧化) 之I蝕刻。如熱濃硫酸、硝酸、亞硝酸、磷酸等。又可、 f於如鹽酸+過氧化氫纟、鹽酸+臭氧水、氟酸+過氧化氫 :之類的過氧化氫、臭氧或氧等具氧化力之混合液。也: 物所钔錯^ δ成可溶性錯合體的物質如氨、帶有胺基白 ,,^ τ 一胺等)、氰化物UCN)等蝕刻。將這物質和過毚 化=混合強化氧化力通常可以加速餘刻。 乳 者t虱水和過氧化氫水及鹽酸和過氧化氫水的混合液* 用的樂液,分別稱為S(M、sC2。一般市售 、鹽酸、式讲& , J ^ 5〜丨·丨· 避虱化氫水的濃度約為20〜35%,和純水以i i ^ $二7的比例混合調製SC 1、SC2。將銅浸泡在此條件 的混合溶液進行蝕刻。 *件下
第5頁 五、發明說明(3) 失i==r[cl、SC2㈣銅,將使銅表面白濁化 刻時也會使=面:Γ酸或熱硫酸等前述之各種藥液韻 鋼表面粗ϋί;;;不而且溫度愈高愈顯著。因餘刻使 弁、4 成朕;度不一。用在配線時產生實質雷Μ卜 平滑:配線接觸不良等問。因此儘量使表面保持 卞α疋飿刻的必要條件。 付 特=以2將再以酸等除去氧化物之銅钱刻方法。如 成氧化物再用稀硫酸或醋酸之心 用稀鹽酸或稀硫酸以座钱刻、成銅氧化膜再 。但是用這些方法銅=丰=等除去, 使氧化膜加厚提高溫度時問題2 ;;'且4寺別疋在為 本發明是為了減少這些問題。Μ ; 的氧化物餘刻銅膜方法可減少鋼除去銅膜氧化後 導體裝置之製造方法、及半導d'銅膜姓刻方法、半 【課題之解決手段】 本發明之特徵為在銅配線時將 及過氧化氫水之混合液(SC1),暴路於pH=8〜u之氨水 氧化膜,然後以稀鹽酸等氧化n成含有乱錯合體之 銅氧化膜選擇性餘刻。在PH=8 ^^弱的酸或稀氨水等鹼將 後本應該將銅進行蝕刻,為了 A液中浸泡氧化膜形成 速飯刻再浸入PH=10〜1 1之 543123 五、發明說明(4) 吁力V 有二錯b广體之氧化膜成長加厚然後再以稀鹽酸等 稀氨水等驗將銅氧化膜選擇性银刻。或 體溶i,·鈇1中1中性胺基酸水溶液將和銅形成之錯合 體公解隹,、、、在中性溶液中仍可將銅氧化膜進行 刻。 又:t:矣:f氧化膜及蝕刻之處理方法使從來銅蝕刻後 不g仏成表面粒糙是困難的方法變 之藥液在短時間内4β ‘古丨如^ ^ τ以女王丑廉核 形成二安定,以化及賺,結果在配線構造的表面 換。之本明之特徵為將銅膜表面和 〜 〜 ΐΐ膜 化氮水之混合液接觸,形成含有二 Ϊ、尚氯。或將銅膜表面和ρΗ=δ〜10或PH4〜10之氨水 之合液接觸,形成含有氨錯合體之氧化膜 水之混合液之步驟。又發明之:== / =以過軋化氫水在銅膜表面形成氧化膜之步驟。前 化膜後的銅膜再暴露於⑽…士之氨水及過氧化 i之混合,形成含有氨錯合體之氧化膜之步驟。 月U銅氧化膜之形成方法是首先使銅膜#σρΗ=8〜i 〇或· 銅氧化=氫水之混合繼,在前述表面形成 曰人Μ,取後再暴露在ρΗ = 10〜丨丨之氨水及過氧化氫水之 此。及,其間可多階段斷續調整ρΗ或連續調整Μ ^發明銅膜之姓刻方法,其特徵在備有以:述任一種銅 羊膜之形成方法在銅膜表面形成含銅之氨錯合體的銅氧
第7頁 543123 五 、發明說明(5) 化膜之步驟,以及自上述奶+ 膜之步驟。上述銅之4 ^ j膜選擇性地除去上述銅之氧化 、^平L 1匕膜可 、, 本發明之半導體裝置之制皮 次或鹼除去。 半導體基板之絕緣膜上步=k方法’其特徵為具有埋入在 配線之銅膜之步驟,、以前聋或接觸孔配線或接觸 前述銅膜上形成含氨錯人I—種銅軋化膜之形成方法在 銅氧化膜從前述銅膜上二埋=鋼氧化膜之步驟,及將前述 述銅氧化膜後之銅除去之步驟。可以在除去前 區域相同深度,也可/二、、x如配線溝或接觸孔側璧附近 表面做為障壁金屬,★二述配線溝或接觸孔上形成金屬膜 表面前述銅膜上形成再二:在:t前述銅氧化膜後之銅膜 同材質所構成,::膜上形成之前述障壁金屬不 暴露於氨水,€可:述銅氧化膜後之銅膜表面 rpm以下之條彼、刚述半蜍體基板以1〇〇〇 rpm以上1600 又太广條件下將銅膜表面暴露在氨水中。 半 導體基tr之半導體裝置之製造方法,其特徵為具有在半 充填^線溝膜上形成之配線溝或接觸孔上堆積金屬以 前述絕緣ίϊί觸孔之^驟’及研磨前述配線金屬以露出 述凹蝕之牛驟’及前述半導體基板之洗淨之步驟及前 屬表面凹二埋入在前述配線溝或接觸孔之前述配線金 述再蝕刻步ϊ:驟’前述研磨步㉟、前述洗淨步驟、及前 又本笋明ί:至少兩種步驟所用的藥液主要成分相同。 &月之半導體裝置之製造方法,其特徵為具有在
543123 發明說明(6) 上堆積金:或金屬化合物之步驟,及触刻前述金 至屬化合物不要部分之步驟,及前述金屬或金屬化合 :堆積之步驟中包含之鍍敷步驟’前述鍍敷步驟 =如鑛敷對像成分及驗或形成錯合體的成分和前述⑽ :去,步驟所用的藥液之主要成分相@,在前述 加之氧化劑可以用過氧化氩水或臭氧纟,在前述藥: =成土以用硫酸或氫氰酸1述不要部分蝕刻除去之 前述藥液中之氧化劑除去之步驟,及前述筚液中 之步驟’更可以將前述氧化劑除去之華液 =相同 又本發明之半導體之製造裝置是二:鍍敷液。 造方法,其特徵為除去包含在前述藥:==裝置之製 將前述藥液中之金屬離子濃度調成和前述二手段’ 鑛敷液使用之手段。 于去…化劑之藥液當成 本發明之半導體裝置,其特徵為在半 述半導體基板上之絕緣膜形成之配線溝^及埋在前 ,在前述配線溝或接觸孔上形成全属: 之金屬膜 ,前述金屬膜表面蝕刻如配線溝或接觸 為卩早1金屬 同深度。前述金屬膜也可介有之前述障辟=附近區域相 配線溝或接觸孔,形成被覆在前述金屬^妾埋入在前述 壁金屬也可以當成埋入在前述配線溝或接觸面上之前述障 銅膜等金屬膜表面愈接近側壁餘刻量命夕 纟、之構造,gp 肩滑落斷面形狀。 里4夕’變成所謂配線
五、發明說明(7) 因此在其上形成之障壁 像這樣的形狀,實施本發明近配線溝側壁膜愈厚。 觸配線在障壁金屬上夕的優點。例如為形成接 域對合偏差-部分進入膜及;形成接觸蝴區 下層配線之障壁金屬之層、,此狀態蝕刻被覆在 膜之蝕刻率較銅膜等之金屬^之二矽氧化膜等之層間絕緣 絕緣之蝕刻在這部分蝕刻較多。酉己為大因此進行層間 !:的徑較平坦部分的徑為大因此= 情形是較深 :易堆積障壁金屬或銅膜層。;:::方位比低,較 障壁金屬。 ^成接觸孔不限於埋入 【發明之實施形態】 以下參照圖面說明發明之實施形態。 本务明適用於半導體裝罟夕 序、單全j ^ ~ m衷置之夕層配線構造,例如穿孔程 =屬鑲肷構造、及雙金屬鑲 (1)有關穿孔程序 弗31疋:成多層配線之半導體基板之剖面圖。以此程序 、=之牙孔配線(或稱接觸配線)是將上層配線及下層配線 之配線。如圖1所示形成埋在下層絕緣膜上之下層配 、,,°積體電路等之半導體元件是在以矽做成的半導體基板 上形成矽氧化膜之層間絕緣膜丨,在其表面形成配線溝 。在此配線溝之側壁形成TaN、wn、τ i N等導電性氮物障壁 ^屬2,銅膜3或以銅為主要成分之合金膜埋入其中。此時 P早壁金屬2僅在配線溝之中存在並沒有在層間絕緣膜1之表 面上形成(圖1 (a))。也可以將障壁金屬越過層間絕緣膜之
第10頁 543123 五、發明說明(8) =在其表面形成。然後將銅膜3表面钱刻使銅膜 車乂層間、纟巴緣膜1之表面為低(圖〗(c ))。 如此在配線溝之上部以濺鍍或CVD等方法將障壁全屬堆 積上去,再以CMP法研磨在配線之上部嵌入一層 ::障壁金屬4之材料可以和障壁金屬2相同也可以ς同(圖 、))。然後將鎢等之障壁金屬6、鋁膜7及依須要依序加 ^導電㈣斷阻8(圖2(a)),將此圖樣化後形成穿孔配線 圖2(b))。然後在層間絕緣層j之上將穿孔配線9以矽氧 化膜等形成之層間絕緣層u被覆(圖3(a))。以CMp法將此 層間絕緣層1丨研磨露出穿孔配線9。其次在層間絕緣層n 上堆積上層之層間絕緣層i 2,然後再埋入上層配線。上層 配線疋由I1早壁金屬1 3、埋在配線溝裡的銅膜丨4及被覆在此 銅膜14表面之障壁金屬15所構成(圖3⑴)。此穿孔配線9 用來連接上下層I線使其通電。本發明適用於在此穿孔程 序中形成障壁金屬4、1 5。即例如障壁金屬4之形成方法 I參照圖1)將埋在絕緣膜i之鋼膜3露出之表面氧化形成銅 乳化膜5(圖1(b))。再用蝕刻法除去銅氧化膜形成不會粗 糙(不會白濁)的表面’在此表面再形成障壁金屬4(圖1(。) )0 (2 )有關單金屬鑲嵌 圖4是形成多層配線之半導體基板之剖面圖。在半導體 基板20上矽氧化膜等層間絕緣膜21、託、29等依次堆積形 成。在各層間絕緣膜21、25、29形成配線溝、接觸孔等, 在其中分別形成下層配線、接觸配線、上層配線等。因為
543123 五、發明說明(9) 在戶"的層間絕緣膜上形成配線溝或接觸孔, 層間、纟巴緣膜表面上形成障壁金屬,妙二° 銅為主成分之合金膜,再用CMP等方法上/積銅或以 ,將以障壁金屬包裹的銅膜埋入配線溝或接觸、表面平坦 w不會白濁)的表面’然後再在此表面形 :曰且
本:明適用於半導體裝置之多層構造形成障壁金屬24 : 28P 埋在層間絕緣膜2 1之下層配線是埋 障壁金屬22、配線溝裡被障壁金屬22包裹:銅=側= 覆在銅膜23上之障壁金屬24所構成。和下層配及被 續’在層間絕緣膜25埋入之接觸 二η 側壁,金屬26、配線溝裡被障壁金屬:开裹 、及被覆在銅膜27上之障壁金屬28所構成。和 鋼膜27 電的接續,在層間絕緣膜29埋人之接觸配線是由埋 於配線側壁之障壁金屬3〇、配線溝裡被障壁金屬3〇勺:: 銅賴、及被覆在銅膜31上之障壁金屬32所構成。匕袤的 因在下層配線之銅膜23形成障壁金屬24可以 士部擴散。X因表面較光滑表面分布不均等影變:广與 又可抑制形成接觸後之電荷集中因此;易發; (3 )有關雙金屬鑲嵌 圖5是形成多層配線之半導體基板之剖面圖。 基板4〇上矽氧化膜等之層間絕緣膜41、45等依次堆積形成
第12頁 543123 五 '發明說明(10) 二=間絕緣膜41、45形成配線溝、接觸孔等,在其中 :別:土:層配線、接觸配線、上層配線等。所有的構造 線漢m鍈嵌相同,因為在所有的層間絕緣膜上形成配 二^在其/堆積銅或以銅為主成分之合金=用 钮二:f或接觸孔。然後依本發明將銅膜表面氧化再用 銅氧化膜形成不會粗糙(不會白濁)的表面,然後 ΐίΐί面形成障壁金屬。即本發明適用於半導體裝置之 夕層構造形成障壁金屬44、。 产:ί絕緣膜41之下層配線是埋在形成於配線側壁之 :二金屬^ '配線溝裡被障壁金屬42包裹的銅膜43、及被 ==上之障壁金屬44所構成。和下層配線介隔-接 == ,在層間絕緣膜45埋入之接觸配線是由 =μ於配線側壁之障壁金屬46、配線溝裡被 46包袤的銅膜47、及被覆在銅膜47上之障壁金屬48所=: 使用本發明方法可得到和單金屬鑲嵌同樣的效果。、 明適用於本發明之半導體裝置形 以上之實施例。 κ攝造 首先參照圖6至圖8說明第1實施例 、本發明之特徵是發現一不會造成表面粗糙之銅膜蝕 法。在銅膜表面形成一含氨錯合之氧化膜,然後用蝕二 將其除去。具體而言,不是先蝕刻銅而是先調整ρΗ = 8ϋ 或Ρ Η 9 1 〇之氨水及過氧化氫水之混合液使鋼膜表面形成 第13頁 543123 五、發明說明(11) ' ' -----1 $厚的氧化膜,然後用稀鹽酸等沒有氧化力的酸或稀氨 7等鹼,此氧化膜蝕刻除去之方法。如前所述,通常用氨] 7和過氧化氫水的混合液(SCI)蝕刻銅時將pH調至丨〇· 5〜丨i - 、。依本發明之實驗得知pH在10以下表面會形成氧化膜,超-過1 0銅將被钱刻等特性。 在此浸泡在調整PH後的SC1 i分鐘使其表面形成氧化膜 \ ,用稀鹽酸選擇性蝕刻此氧化膜時銅之蝕刻量如圖6所示 。圖6之縱軸表示蝕刻量(nm),橫軸表示抑。如圖6所示銅 ,面浸泡在約18%之過氧化氫水形成氧化膜,此時之蝕刻 量約4 nm二然而加入氨水中和pH = 7時幾乎沒有氧化,再加 入更多的氨水,當pH超過8時蝕刻量增加,丨〇約丨丨~ ^ 2 nm。pH超過10產生深藍色的氨錯離子溶解。圖7(a)是處理 前之銅表面,(b)是在pH = 9. 5之氨水及過氧化氫水混合^夜 氧,1分鐘後^用鹽酸蝕刻後之銅表面。圖8(a)是在〇· 2 - 之氨水及過氧化氫水混合液蝕刻後之銅表面。對照來考圖 8(b)是鹽酸及過氧化氫水混合液(8〇它)蝕刻後銅表面之 SEM像。從圖得知用調整pH後的氨水及過氧化氫水可尸到 表面不會粗糙之蝕刻方法。 $ 為了在微影蝕刻時位置可以確實對合期望有3〇〜5〇㈣的 #刻&期望㈣時間儘量縮短。只用過氧化氯水處 理可以得到較厚的氧化膜,㈣50 nm帛要12〜13分鐘的處 理時間。因此用PH = 8~l〇,最好是PH = 9〜10的溶液處理。尤 其疋p Η - 1 0附近的溶液處理5 〇 n m的钱刻只要4分鐘。 然而不是只有調整pH值就可以,如圖6所示;7 =如將銅--
第14頁 543123
浸泡在PH調到9〜ι〇 5 化鼠水和膽酸之(昆人 要性。 之過氧化氫水和K〇H之混合液或過氧 液也幾乎不會氧化。這顯示用氨的重 以下說明第2實施例。 如第1實施例所述銅 將銅浸泡在pHq0之ςΓ1 , ^取好疋在30〜50 nm。然而 太杏#存丨眩# 之%1 1为鐘只能得到1 2 rim的蝕刻。在 旦二;/ D =明f增加钮刻量表面又不會粗糙的方法。一
形i氧化^化氫水溶液或pH=8〜1〇之如之銅膜表® 片 、接考再將此銅膜浸泡在ρΗ=10〜11之SCI。通 :V以乂1 ϊ蝕刻的條#,因•在表δ已預先形*氧化港 艾了以形成更厚的氧化膜。 人:ΪΪ氧化氫水(35%):氨水(35%):純水=1〇:3:100之混 二比此合成ρΗ = 1 0之溶液,將銅膜浸泡在此溶液30秒後接 f將組成比改變成1:1:10 (ρΗ=1 0.5) ’再浸泡1分30秒在 銅膜卜犯4·、® r» 、化成更厚的氧化膜,然後再用稀鹽酸只將含氨錯洽 ^ 乳化膜蝕刻,銅蝕刻量可達5 0 nm。在此浸泡在第1實 &例的溶液中處理時間合計2分鐘約可得到2倍的蝕刻量, 可縮短處理時間。
以下參照圖9及圖1 〇說明第3實施例。 在本實施是以例如圖1埋入之銅配線或圖3至圖5所示下 f配線為對像蝕刻實際的銅配線。浸泡在pH = l 0之SCI (過 氧化氫水:氨水:純水=1 〇 : 3 : 1 0 0 ) 1分鐘後再用2 0 %鹽酸稀釋 5 〇 供*> 口 <稀鹽酸將表面之氧化膜除去,如此反復三次將銅蝕 刻約3 5〜4 0 n m的0 · 2 5 // m線和空間配線之剖面圖如圖9所
第15頁 543123 五、發明說明(13) 示。在圖9中半導體基板5〇上形成層間絕緣膜5 絕緣膜5 1上形成障壁金屬以, 在層間 銅膜53埋入此配線溝54屬針、侧土上堆積配線溝54 ’ 开成ί化膜再钱刻處理形成不粗糙的表面,然後 全屬,CMP算Λ Λ立 將TaN或WN等堆積第2障壁 至屬#方法形成障壁金屬55。 如圖9所示蝕刻鋼鍈53形成不粗糙的表面 f广f量愈,,變成所謂配線肩滑落斷面:狀广因此在 於這種形狀用本發=膜的厚度愈大。對 好處的模式剖面圖 广 :夕子處。即圖1〇是說明這 銅配線,如圖l〇(b)所-上? 圖9所示謂配線肩滑落之 下μ « 2 千坦之銅配線。為形成將上芦配堍拉, 下層配線之接觸孔配線必須在下盾配線接在 上形成接觸孔(穿孔)。如圖所示^成隹積層間絕緣膜 在銅配線上面形成之障壁全屬步成 觸配線將接觸孔 刻被覆下層進入層間絕緣膜…狀態兹 二氧化膜)之㈣速率比銅膜大=絕緣膜 :::較、多’如圖丨。“)、圖1〇⑻虛絕緣膜 如圖10(a)深的部分&苴、、突声,Μ不開口0 J度為b,。因材質決定二二率。圖°(b)深的部分a,其 =,’深的部分之直徑 a )。換言之在圖10(b)深的部 —:直位為 刀〜成一袋狀空間, 第16頁 543123 五、發明說明(14) 這地方的方位比(b,/a,)明顯地較圖丨〇(a)深的部 比(b/a)為大,因此在圖1〇(b)之接觸孔堆積 用鍵敷的方法將銅埋入接觸孔不易形成片狀銅 10(a)之接觸孔堆積障壁金屬形成片狀銅膜就容 / 當然這不限於銅,所有半導體之 / ° 可適用。不只在金屬膜上埋入障壁金】金屬, 層或直接堆積層間絕緣膜也可適用。 心成障壁 以下說明第4實施例。 將銅配線浸泡在ΡΗ=1 〇之SC1 (過氧化氫水··氨水. 1 0:3:1 00 ) 30秒再鐘後再浸泡在pH=1〇. 5(混合比卜之 例使其表面氧’然後用35%過氧化氯·水以3/10之 比例用純水稀釋溶液除去表面之.氧化膜,可以蝕刻約5〇 :、1 第3實施例相同的方法在上層用濺鍍法或CVD等 ΪΪΓ円=堆積第2障壁金屬。然後再用CMP法研磨 形成如圖3所示配線溝。 以下參照圖11說明第5實施例。 曰^本實施例說明適用於本發明之銅配線形成步驟。圖i! 疋龙明銅配線形成程序圖。如圖所示銅配 "首先①在層間絕緣膜上形成配線溝。其次②在配2溝; =Ρ及側面用濺鍍法或c ν D等方法將T a Ν或㈣等堆積障壁金 1田rif③用賤錄法或CVD等方法將銅埋入配線溝。然後 ^用CMP法只研磨鋼或研磨銅及障壁金屬形成埋入層間絕 、,象膑之銅配線。然後⑤將CMP後之晶圓洗淨,若有必要⑥ 銅钱刻曰曰曰圓的斜切部及裏面然後洗淨。最後⑦進行本發明 543123 1、發明說明(15) 之銅凹蝕處理。 可在銅表面形成氧化膜研磨時可保護内部 苴:=:cmp之研襞。又通常在cmp後在同-裝置或 至,、他装置用滾筒海綿或懸掛海綿等物理方法
=用驗性藥⑨,粒子洗淨效果顯著。本發明之藥液其PH 。鹼性,對除去CMP後之研磨殘留粒子(鋁或矽等)'很有效 。:=i r:D等方法將銅堆積在晶圓的斜切部及裏面 積時曰二钭:等方法堆積的銅當成底層用鍍敷法堆 切部的銅。晶圓的斜切部及裏面是和;:;ί 造/置之媒介有可能污染其他晶《。二ί 。也可以在cmI ί在晶圓的斜切部及裏面的銅蝕刻洗淨 染=;:;;;:二有;能彻時再度被銅污 裏面,以迴轉m置轉7且圓°為/寞同/洗+淨斜切部及 化氫水之混合r…肖酸ΐ: “仗晨面贺出鹽酸和過氧 以溶解銅。然而此方法❹;;酸:氧化力強的酸 鋼只在晶圓邊缘附、斤气几處後會產生表面裝置部分的 或蝕刻中2生的HC1、:問題。這可能是從藥液中氣化 局部氧化。 、 x、S0x等氣體殘留在銅表面促使 處稀琉酸等氧化力弱㈣ 任日日0邊緣附近銅膜變薄的問題。 第18頁 五、發明說明(16) :t免這問題可採用將晶圓旋轉從正面用純 :在斜切部裝設嘴出藥液的喷嘴處理斜切 :中:寞: ^出藥液處理裏面的方法。但是這又有必須== ::贺嘴廷使製造裝置複雜提高裝置價格 =面看若從表面沖洗純水往後就不能回收 循環钱刻液因而增加藥液的使用量。
但若用本發明的方法CMP處理後的銅表面預先 問題。因此在形成銅配線時如圖i j所示銅CMp =、 到銅凹蝕(⑦)全部步驟可用同一藥液,且所有程序 一裝置内進行。 你J 可用同一藥液就表示製造半導體裝置時有簡略構造的好 ,二在同一製置内連續處理就不必在每一步驟進行乾燥可 提高流程順暢的優點。例如圖丨4是上述同一室内進行=導 體製裝置之概略圖,以圖丨丨所示程序說明銅配線形成步驟 。百先①在層間絕緣膜上形成配線溝。其次②在配線溝的 底部及側面堆積障壁金屬。然後③用鍍敷將銅埋入配線溝 。此步驟在銅鍍敷槽61進行,然後④用CMp法只研磨銅或 研磨銅及障壁金屬形成埋入層間絕緣膜之銅配線。此步驟 在銅鍍敷槽62進行,然後⑤將CMP後之晶圓洗淨,此步驟 在銅鍍敷槽63進行。而後,進行⑥!斜切部·裏面銅蝕刻及 洗淨。此一步驟係在蝕刻槽6 4進行。最後⑦銅凹蝕處理在 钱刻槽64進行。這些銅鍍敷槽6 1、CMP裝置62、CMP洗淨裝 置6 3、蝕刻槽6 4、及處理槽6 5全部配置在室6 〇内在此可實 543123 五、發明說明(17) 施銅配線之形成之步 在此室60各内部裝 藥液集中到處理槽6 5 整硫酸濃度再送回鑛 可以做到資源回收。 圖15是半導體製造 造裝置具有鍍敷槽Η 是由濃度調整部及調 整將純水加入從钱刻 合體成分濃度的藥液 敷液。然後將此供入 的藥液相較於在鍍敷 餘刻室6 4排放的藥液 部即可。 將鑛敷處理 銅水溶液選用 刻銅或氧化銅 為姓刻樂液和 。用蝕刻後藥 驟。 置裡從銅鍍敷槽6 1及蝕刻槽6 4排出的 ’監視銅濃度排除臭氧等氧化劑,調 敷槽6 1。如此本發明半導體製造裝置 裝置之概略圖。如圖14所示半導體製 、飯刻槽6 4、及處理槽6 5。處理槽6 5 整鍍敷液之鍍敷部所組成,供應且調 槽6 4排出的藥液、或調整形成鹽·錯 ’調整後的藥液供入鍍敷液部當做鍍 鑛敷槽(鍍敷室)6 1。從|虫刻室6 4排放 至6 1使用過的鑛敷液量少時只須整從 ’而使用過的鍍敷液直接回收到鍍敷 1入同一裝置内時所使用的鍍敷液若是硫酸 ^ 、若是氰化銅水溶選用氫氰酸,如此蝕 後的溶液和鍍敷液成分相同對程序有利。因 使用過的鍍敷液成分相同可以同時排放處理 液再進行鍍敷可得銅的利用效率極高的製程 金i ϊ:;員::ΐ或氫氰酸等氧化力弱的酸不容易蝕刻 後變成tθ >、Μ予軋化力之氧化劑,使用反應後或分解 10%之硫酸銅水溶、夜六、軋較好。例如在鍍敷液加入 a,以10/。之硫酸(+過氧化氫水或臭氧)
第20頁 543123 五、發明說明(18) 蝕刻銅或銅氧化物,蝕刻液中用離子濃度 等線内監視銅濃度,超過〗〇 %時則回收 里、吸光度 以用和鍍敷液不同濃度的硫酸,也可以 。當然也可 不容易只增加銅漠戶,#林伯义曲 衣使用。又因 田%田芏从山 取好使銅濃度高到硫醆濃择 取後用活性奴過濾器或訂燈照射將蝕刻液辰度以上。 臭氧分解,監視銅濃度或硫酸濃度加入硫式,氧化氫或 處理或以逆滲透用半透膜處理濃縮作成丨〇% 3 '、、水,加熱 液。然後加入鍍敷必須的添加劑鍍敷時使 爪酸銅水溶 時調整使用過的鑛敷液濃度。可將濃度調整過二匕:寺也可同 一點加入鍍敷液内。當然濃度監視或 =液一點 液濃縮機構不限於以上所提及之物。 剧除去機構、藥 此種敍刻後的溶液當成鑛敷液再 於銅’如AU、Ag、Ti箄所古π蚀畆 序及裝置不限 . g 11 4所有可鍍敷的金屬都可適用。 以下芩照圖1 2說明第6實施例。 = 12 =明銅凹银時氨處理晶圓配線電阻和晶圓迴轉數 H Ϊ ^ 在此實施例以迴轉式葉片裝置進行銅凹 =V 私,(1) . NH40H:H2 02:DIW ( 30:1 00:1。。。),60 秒, rpm (2) .NH4〇H:H2〇2:DIW (1〇〇:1〇〇:1〇〇),60 秒, iOOO rpm,(3) .HC 1 ( 3 0:1 000 ),5 秒,1〇〇〇 rpm 處理可 二=約吁⑽的銅。但以鹽酸處理後的銅表面氧化加速。 ’’5 、面氧化造成配線實際有效的銅減少,配線截面積降低 =,電阻上升等問題。又銅表面和上部障壁金屬之間形成 5 ^,膜,裝置上上部的穿孔的接觸電阻上升,可能因產 生電容造成延遲的原因。在程序上上部障壁金屬形成時控
543123
制凹钱處後的時間必須迅 理時可能發生剝落等問題 然而在鹽酸處理後進行 水會餘刻銅’過度處理造 葉片裝置以氨水蝕刻銅知 圖形是8吋矽晶圓上〇. 35 m Ω )在晶圓面内1 9薄片形 分鐘後其配線電阻(Ω )以 銅被姓刻截面積減少電(I旦 钱刻。此時晶圓面内蝕刻 ,均一性好則分布不均小 小,1 4: 7 5 r ρ πι附近有極小 有相同的分布不均。 速在上部堆積障壁金屬或CMp處 〇 氨水處理,可以抑制氧化。但氨 成表面粗糙的原因。使用迴轉式 I虫刻特性依迴轉數改變。以下的 # m之銅配線(配線電阻約3 4 2 成後將銅用3. 5%之氨水蝕刻約j 〇 晶圓迴轉數為參數作圖。配線的 上升。3x 104 πιΩ表示鋼完全被 之均一性不良電阻上升分布不均 。超過1 0 0 0 rpm以上分布不均變 值,在 1 6 0 0 rpm 和接近100() rpm 又在2 0 0 0 rpm下也可進行蝕刻,但400 nm的鋼完全被姓 刻。因為只希望在表面處理所以這種高速餘刻條件不是很 適宜。迴轉數超過1600 rpm以上可預知蝕刻速率會上升, 因此處理條件以1 6 0 0 rpm以下為宜。是以,為抑制氧化之 氨處理,以1000 rpm以上1600 rpm以下為宜。
在此上述凹蝕程序後實際進行氨處理,在清潔室環境下 處理後保存2 4小時之銅表面相對於用鹽酸最後加工氧化呈 茶褐色,用氨最後加工則具有處理前同樣的金屬光澤。處 理條件為(1 ) · NH40H : H2 02 : DIW ( 3 0 : 1 0 0 : 1 0 0 0 ),60 秒, 1 0 0 0 rpm,(2) · NH40H:H2 02:DIW ( 1 0 0:1 0 0:1 0 0 ),60 秒, 1000 rpm , (3) · HC1 (30:1000) , 5 秒,1000 rpm , (4) ·
第22頁 543123
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Claims (1)
- 543123 ^ ^ 修」^ n ^ - Η " 、4-;丨案號89124469 办年 > 月 日 修正不_ (—— 六〜肀圍 1. 一種銅氧化膜之形成方法,其特徵為在銅膜表面接觸 以ρΗ = 8〜10或ρΗ = 9〜10之氨水及過氧化氫水之混合液,而形 成含有銅氨錯合體之氧化膜。 2. —種銅氧化膜之形成方法,其特徵為包含在銅膜表面_ 接觸以ρΗ = 8〜10或ρΗ = 9〜10之氨水及過氧化氫水之混合液, 而形成含有銅氨錯合體之氧化膜之步驟,及將前述表面形· 成有氧化膜之銅膜暴露於ρΗ==10〜11之氨水及過氧化氫水之 混合液之步驟。 3· —種銅氧化膜之形成方法,其特徵為包含以過氧化氫 水在銅膜表面形成氧化膜之步驟,及將上述形成有氧化膜 之銅膜暴露於ρ Η = 1 0〜1 1之氨水與過氧化氫水之混合液中, 而形成含銅氨錯合體之氧化膜之步驟。 4. 一種銅膜蝕刻方法,其特徵為包括以根據申請專利範 圍第1〜3項中任一項之銅氧化膜形成方法,在前述銅膜表 面形成含銅氨錯合體之銅氧化膜的步驟,以及自前述銅膜 選擇性地除去前述銅氧化膜的步驟。 5 .如申請專利範圍第4項之銅膜蝕刻方法,其中係以酸 或鹼除去前述銅氧化膜。 6. —種半導體裝置之製造方法,其特徵為具有在半導體 基板上之絕緣膜中所形成之配線溝或接觸孔内埋入供形成 配線或接觸配線之銅膜之步驟,及藉由根據申請專利範圍| 第1項至第3項中任一項之銅氧化膜之形成方法在前述銅膜 表面形成含銅氨錯合體之銅的氧化膜之步驟,及將前述銅 氧化膜從前述銅膜上選擇性除去之步驟。67665-920212.ptc 第26頁 543123 案號 89124469 年 月 曰 修正 六、申請專利範圍 7. 如申請專利範圍第6項之半導體裝置之製造方法,其 中經除去前述銅氧化膜後的前述銅膜表面,係以愈接近前 述配線溝或接觸孔側壁的區域愈深之方式經蝕刻。 8. 如申請專利範圍第7項之半導體裝置之製造方法,其 中在前述配線溝或接觸孔,或配線溝及接觸孔和前述埋入 之銅膜之間介有一層障壁金屬。 9. 如申請專利範圍第8項之半導體裝置之製造方法,其 中復具有在除去前述銅氧化膜後的前述銅膜上形成一層障 壁金屬之步驟。 傷 10. 如申請專利範圍第9項之半導體裝置之製造方法,其 中前述配線溝或接觸孔,或配線溝及接觸孔和前述埋入之 銅膜之間介有之前述障壁金屬,和前述銅膜上形成之前述 障壁金屬係由不同材質所構成。 11. 如申請專利範圍第10項之半導體裝置之製造方法, 其中復具有將除去前述銅氧化膜後的前述銅膜暴露在氨水 之步驟。 1 2.如申請專利範圍第1 1項之半導體裝置之製造方法, 其中係將前述半導體基板以1000 rpm以上1600 rpm以下之 迴轉條件,將銅膜表面暴露在氨水中。67665-920212.ptc 第27頁
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CN109545737A (zh) * | 2017-09-22 | 2019-03-29 | 株式会社斯库林集团 | 基板处理方法及基板处理装置 |
CN113661275A (zh) * | 2019-05-09 | 2021-11-16 | 纳美仕有限公司 | 复合铜部件 |
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JP2001210630A (ja) | 2001-08-03 |
KR100426554B1 (ko) | 2004-04-08 |
JP3907151B2 (ja) | 2007-04-18 |
US6818556B2 (en) | 2004-11-16 |
TWI225277B (en) | 2004-12-11 |
US20030001271A1 (en) | 2003-01-02 |
KR20010074557A (ko) | 2001-08-04 |
US6261953B1 (en) | 2001-07-17 |
TW589687B (en) | 2004-06-01 |
US20010034125A1 (en) | 2001-10-25 |
US7183203B2 (en) | 2007-02-27 |
TW200300988A (en) | 2003-06-16 |
US6475909B2 (en) | 2002-11-05 |
US20050064700A1 (en) | 2005-03-24 |
TW200300989A (en) | 2003-06-16 |
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