TW201631207A - 利用硬遮罩結構之溝槽圖樣濕式化學銅金屬填充 - Google Patents
利用硬遮罩結構之溝槽圖樣濕式化學銅金屬填充 Download PDFInfo
- Publication number
- TW201631207A TW201631207A TW104142553A TW104142553A TW201631207A TW 201631207 A TW201631207 A TW 201631207A TW 104142553 A TW104142553 A TW 104142553A TW 104142553 A TW104142553 A TW 104142553A TW 201631207 A TW201631207 A TW 201631207A
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- Prior art keywords
- copper
- layer
- hard mask
- dielectric
- deposition
- Prior art date
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 105
- 239000010949 copper Substances 0.000 title claims abstract description 105
- 239000000126 substance Substances 0.000 title claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 title claims description 45
- 239000002184 metal Substances 0.000 title claims description 45
- 238000011049 filling Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 65
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 230000004888 barrier function Effects 0.000 claims abstract description 29
- 238000007747 plating Methods 0.000 claims abstract description 27
- 230000008021 deposition Effects 0.000 claims abstract description 21
- 239000004065 semiconductor Substances 0.000 claims description 14
- -1 Cu(II) ions Chemical class 0.000 claims description 13
- 239000003989 dielectric material Substances 0.000 claims description 13
- 238000007772 electroless plating Methods 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 9
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910004166 TaN Inorganic materials 0.000 claims description 3
- 239000010953 base metal Substances 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 2
- 229960003681 gluconolactone Drugs 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 235000010356 sorbitol Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 claims 1
- 229940119177 germanium dioxide Drugs 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 238000000059 patterning Methods 0.000 abstract description 2
- 239000002659 electrodeposit Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 34
- 238000000151 deposition Methods 0.000 description 22
- 230000008569 process Effects 0.000 description 15
- 238000009713 electroplating Methods 0.000 description 10
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 9
- 238000005240 physical vapour deposition Methods 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 230000009977 dual effect Effects 0.000 description 7
- 238000005137 deposition process Methods 0.000 description 6
- 238000001459 lithography Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000001020 plasma etching Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 241000724291 Tobacco streak virus Species 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 238000000224 chemical solution deposition Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 229910000521 B alloy Inorganic materials 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JJFNJZGXHWYGMQ-UHFFFAOYSA-N [Ni].B#[Co] Chemical compound [Ni].B#[Co] JJFNJZGXHWYGMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229940032330 sulfuric acid Drugs 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
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Abstract
本發明係關於一種用於將銅電沈積至結構中之溝槽圖樣中的方法,該方法包括以下步驟:在介電基板層上方形成經圖樣化硬遮罩層;藉由使用穿透該經圖樣化硬遮罩之蝕刻來圖樣化該介電層,視情況,在該經圖樣化介電基板層及該硬遮罩層之表面上方形成障壁層及/或襯墊層;藉由濕式化學鍍方法在該障壁層及該硬遮罩層上方形成基礎銅晶種層以為銅之後續電解沈積提供充足的電導率;及將該介電基板浸入至電解銅鍍系統中之電解銅鍍浴中以將銅電沈積至該經圖樣化介電基板層中。該硬遮罩僅需要在銅沈積之後移除。
Description
本發明係關於用於使用硬遮罩及銅晶種層藉由濕式化學無電式電鍍方法及電解銅沈積將銅電沈積至溝槽圖樣中以填充溝槽圖樣的方法。根據本發明之方法尤其適用於微晶片及類似者的製造中之雙鑲嵌及TSV(矽穿孔)電鍍。
本發明係關於半導體結構及半導體製造之方法。更具體而言,本發明係關於用於改良電解銅沈積以填充溝槽圖樣之半導體結構及半導體製造之方法。
製程步驟通常涉及圖樣化溝槽特徵及將溝槽特徵蝕刻至金屬硬遮罩中,繼之以將圖樣轉印至底層材料中之蝕刻步驟。
此構造為此項技術中已知的,且(例如)在US 2007/0205482 A1、US 2008/0265426 A1及US 2008/096389 A1中予以解釋。此等文件中無一者解決了具有高縱橫比之凹入結構之銅填充的難題。
在半導體製造中,後段製程(Back End of the Line;BEOL)銅互連件縮放使用溝槽優先金屬硬遮罩(Trench First Metal Hard Mask;TFMHM)製程來維持圖樣保真度及在製造製程期間(例如)自微影至電漿蝕刻的控制。此項技術中已知且在美國專利第8,796,150 B2號中描述之用於選擇溝槽優先硬遮罩(TFHM)的一個動機為消除在紋路(溝槽)
側壁以及通孔兩者中均可見之導致低k介電質損害的氧型電漿灰之通過。低k介電材料具有比二氧化矽低的介電常數。在處理期間,金屬硬遮罩可包括沈積於介電質硬遮罩薄膜上之氮化鈦(TiN)薄膜。可使用含有機物之薄膜在TiN薄膜上形成微影圖樣。然而,對互連件結構之溝槽造成的非所要結果可在以上或後續處理期間出現。因此,TFHM整合引起關於金屬硬遮罩(例如,TiN)沖蝕及在微影返工及雙鑲嵌蝕刻兩者期間與電漿相互作用之新難題。舉例而言,在典型的返工過程期間,電漿化學反應既可改質表面亦可減小TiN薄膜厚度,此情形隨後在互連件處理期間之雙鑲嵌蝕刻製程步驟期間導致更寬的臨界尺寸。因此,此導致橫越晶圓直徑之不均勻性的非所要增加。此外,TiN沈積與微影之間可能出現較長的製程佇列時間,且由此,金屬的TiN薄膜形成非所要自然氧化物,該等氧化物以使得對橫越晶圓之特徵之臨界尺寸均一性(CD)的控制變得更加困難之方式影響微影及與碳氟化合物反應。另外,此等機制可產生影響整體圖樣保真度之實體缺陷。
多層介電質堆疊之電漿蝕刻使得蝕刻單元過程在維持不同層之間的蝕刻選擇性且同時產生所得通孔及溝槽特徵之可接受輪廓方面具有挑戰性。
為了解決下游過程相容性,以低k介電材料製造之雙鑲嵌特徵可含有犧牲層(諸如,介電質或硬遮罩),其在銅之化學機械拋光期間用於在金屬化之前保持原位且僅在金屬化之後經移除。然而,溝槽圖樣中朝向高縱橫比之趨勢使得此迄今使用之方法愈來愈困難。高縱橫比因雙鑲嵌流程中犧牲層(例如硬遮罩)之存在而進一步增加,且使物理氣相沈積製程在提供連續保形沈積方面之能力具有挑戰性。
為了克服物理氣相沈積之視線限制,利用替代途徑(諸如再濺鍍障壁層及襯墊層)來增加通孔及溝槽之側壁上之障壁層及襯墊層的覆
蓋度。具有良好黏著力之連續晶種對於確保經電鍍之銅完整填充至雙鑲嵌特徵中為必要的。
因而,將需要提供可靠的且不需要在金屬化步驟之前移除硬遮罩之用於使用銅進行圖樣填充之方法。
此目標由用於將銅電沈積至結構中之溝槽圖樣中之方法解決,該方法包含以下步驟(i)提供基板,該基板包含至少一個導電特徵、該導電特徵上之至少一個介電層及最外部介電層上之硬遮罩;(ii)在該硬遮罩層及該至少一個介電層中形成凹入結構;(iii)在所形成之凹入結構的表面上方形成障壁層及視情況形成襯墊層;(iv)藉由濕式化學鍍方法在障壁層或視情況之襯墊層上方形成基礎銅晶種層,以為銅或銅合金之後續電解沈積提供充足電導率;(v)將基板浸入至電解銅鍍系統中之電解銅或銅合金電鍍浴中,其中基礎金屬晶種層經連接作為陰極,該系統進一步包含銅金屬源及陽極;及在該陽極與該基礎金屬晶種層之間施加電壓,使得電流在其間流動足以使銅填充該等凹入結構之時間;(vi)移除硬遮罩包括移除沈積至硬遮罩上之經電沈積之銅。
(a)‧‧‧經圖樣化介電基板層
(b)‧‧‧介電層
(c)‧‧‧硬遮罩層
(d)‧‧‧銅晶種/薄銅晶種層
(e)‧‧‧後續電解銅沈積
圖1展示根據先前技術之方法之用於銅填充溝槽圖樣的方法。
圖2展示根據本發明方法之用於銅填充溝槽圖樣的方法,該方法包括對保形且薄的銅晶種層之無電式沈積。
適用於根據本發明之方法的基板材料較佳地選自矽、矽基板上之低k介電材料及玻璃。由此類材料製成之電子器件包含微晶片、玻
璃插入件及其類似物。此類基板材料中之凹入結構需要塗佈或填充有通常藉由電鍍沈積之金屬。最相關之金屬為經電鍍之銅。
根據本發明之方法的一個特定應用為將金屬電鍍至極精細凹入結構中,該等極精細凹入結構經蝕刻至矽基板或矽基板上之低k介電材料中。典型的低k介電材料在此項技術中已知且包含氟摻雜之二氧化矽、碳摻雜之二氧化矽、多孔二氧化矽、多孔碳摻雜之二氧化矽、聚醯亞胺、聚降冰片烯、苯并環丁烷、PTFE及旋塗式基於聚矽氧之聚合介電質,諸如氫-倍半矽氧烷及甲基-倍半矽氧烷。
此類極精細凹入結構可為盲孔(僅具有一個開口)、通孔(在基板兩側上均具有開口)以及溝槽(線型圖樣及類似者)。此類凹入結構通常具有範圍在(例如)5nm或10nm至幾百微米或甚至幾百毫米內之幾何尺寸。本發明之方法尤其適合於形成溝槽。
典型的應用為雙鑲嵌應用,其中凹入結構形成於矽及/或低k介電材料中且具有奈米或較小微米範圍中之開口大小。銅晶種層可具有範圍在1nm至200nm(較佳地至多20nm)之厚度。
另一應用為填充矽穿孔(TSV),該等矽穿孔為矽基板上之矽及/或低k介電材料中的盲孔。TSV之開口典型地在微米範圍內,且銅晶種層可具有高達幾百奈米或甚至1微米或1微米以上之厚度。
所有此等應用均需要銅晶種層之均勻厚度分佈及光滑外表面。
根據本發明之方法尤其有利於對具有高縱橫比(亦即,至少3比1(更佳地10比1且甚至更佳地高達100比1)之深度與寬度縱橫比)之凹入結構之銅填充。
在許多情況下,必須抑制該經電鍍金屬進入基板材料中或基板材料進入經電鍍金屬中之不希望的擴散及相關過程以便獲得及/或維持最終電子器件之所需特性。因此,藉助於一或多個障壁層分隔經電鍍金屬,該等障壁層藉由以下方法沈積:諸如化學氣相沈積(CVD)、
物理氣相沈積(PVD)及原子層沈積(ALD)之氣相方法及前述者之電漿增強型方法或諸如無電式電鍍之濕式化學製程。在兩個或兩個以上個別障壁層材料之堆疊的情況下,僅最外部障壁層將與無電式銅鍍浴接觸。在兩個或兩個以上個別障壁層之堆疊的情況下,單一障壁層材料或最外部障壁層材料係選自鈷、鎳、釕、鎢、鉬、鉭、鈦、銥、銠及前述者之合金。
該「前述者之合金」包含諸如氮化鎢、氮化鉭及氮化鈷(諸如Co4N)之氮化物以及諸如鈷-及鎳-磷或-硼合金、三元鈷-及鎳-磷合金及三元鈷-及鎳-硼合金(例如,Ni-Mo-P、Ni-W-P、Co-Mo-P、Co-W-P、Co-W-B)之磷化物及硼化物。
該障壁層或最外部障壁層之厚度在若干障壁層之堆疊的情況下通常具有1nm至20nm之範圍內之厚度。
目前在半導體製造中之小型互連件特徵之產生期間使用硬遮罩。以往,金屬硬遮罩將在蝕刻步驟、視情況之障壁層及襯墊層及晶種層之沈積以及電解鍍銅步驟期間保持原位,且隨後在CMP(化學機械拋光)期間經移除。然而,在新生代半導體特徵中,金屬硬遮罩必須在蝕刻步驟之後且在障壁/襯墊/晶種之沈積之前經移除,主要係由於作為晶種之PVD(物理氣相沈積)銅之可接受覆蓋度的問題。金屬硬遮罩之移除作為凹入結構之金屬化前之額外步驟係不希望的的。
本發明之獨特優勢為,不必在步驟(iii)中形成基礎銅晶種層及在步驟(iv)中用銅填充凹入結構之前移除金屬硬遮罩。
半導體基板上之凹入結構之形成通常執行如下。
在於基板上形成至少一個導電特徵之後,將至少一個介電層塗覆於導電特徵之表面上。通常塗覆第一介電層及第二介電層,其中兩個介電層具有不同物理機械特性。
接下來,藉由首先在介電材料之外部表面上形成毯覆式硬遮罩
層將至少一個凹入結構(例如,溝槽)形成至介電層材料中。利用習知沈積製程形成毯覆式硬遮罩材料。
在形成硬遮罩材料之毯覆式層之後,利用習知沈積製程(諸如,CVD、PECVD、旋塗式塗佈法、化學溶液沈積或蒸發)在硬遮罩材料頂上形成光阻劑。光阻劑可為正型色調材料、負型色調材料或混合材料,熟習此項技術者熟知該等材料中之每一者。接著光阻劑經受微影製程,該微影製程包括將光阻劑曝露於輻射圖樣及利用習知抗蝕劑顯影劑使經曝露抗蝕劑顯影。微影步驟在硬遮罩材料頂上提供界定凹入結構之寬度的經圖樣化光阻劑。
在提供經圖樣化光阻劑之後,利用一或多個蝕刻製程將凹入結構轉印至硬遮罩材料中且接著隨後轉印至介電材料中。可在將凹入結構轉印至硬遮罩中,形成經圖樣化硬遮罩之後,利用習知剝離製程立即剝離經圖樣化光阻劑。替代地,可在將通孔圖樣轉印至第二介電材料中之後剝離經圖樣化光阻劑。用於轉印通孔圖樣之蝕刻可包含乾式蝕刻製程、濕式化學蝕刻製程或其組合。術語「乾式蝕刻」在本文中用以指代諸如反應性離子蝕刻、離子束蝕刻、電漿蝕刻或雷射切除之蝕刻技術。
由於凹入結構按比例縮放至小於100nm之體系中,因此亦需要按比例縮小沈積於此等特徵中之銅晶種的厚度以防止在電沈積步驟之前夾止。於具有相對高的薄層電阻之薄銅晶種上電鍍由於電鍍池中之終端效應而具有挑戰性,由此橫越半導體基板直徑之壓降引發電鍍層厚度之較大不均勻性且亦可導致特徵內之空隙。
圖1中展示此情況。圖1.1展示溝槽圖樣,其包含經圖樣化介電基板層(a)及具有在經圖樣化介電基板層上方之硬遮罩層(c)的介電層(b)(凹入結構為溝槽)。圖1.2描繪藉由PVD沈積之銅晶種(d)。如變得顯而易見,溝槽圖樣頂部處之開口相對較小。此情形導致不完全的由下
而上填充、在藉由電解沈積技術用銅完全填充特徵之前空隙及夾止的風險。
出於此原因,在使用PVD技術產生銅晶種層時,需要在晶種層形成(圖1.4)之前移除硬遮罩(圖1.3),以便減小縱橫比且確保晶種層具有用於完全電解銅填充之適合開口。硬遮罩移除之此額外步驟並非所要的,尤其因為其可能尤其在使用低k材料時導致基板材料之損害,低k材料在硬遮罩移除期間易於機械損害。
不同於經PVD沈積之銅,藉由濕式化學鍍製程沈積之無電式銅並非定向製程,且可在因使用金屬硬遮罩所引起的較高縱橫比及/或變形的凹入特徵上沈積保形層(圖2)。
圖2.1展示溝槽圖樣,其包含經圖樣化介電基板層(a)及具有在經圖樣化介電基板層上方之硬遮罩層(c)的介電層(b)。介電層可額外地及視情況具備障壁層及/或襯墊層(未展示)。熟習此項技術者熟知此等層之使用及性質。障壁層抑制銅擴散至包含結構之介電層中,且襯墊層促進晶種層與底層之間的黏著。
圖2.2描繪藉由根據本發明之方法的無電式金屬化步驟沈積之銅晶種(d)。如自圖2.2可見,具有均勻厚度分佈之薄銅晶種層(d)可沈積於整個表面上方,保留用於後續電解銅沈積(e)之足夠大的開口。因此,可在金屬化(圖2.3中所展示)之前省略金屬硬遮罩移除步驟,從而允許更容易的整合。
另外,由於特徵變得更小且需要極薄晶種層(諸如無電式銅),因此半導體基板之薄層電阻可顯著上升。此情形導致終端效應增大,其可引起電沈積之均一性的問題。終端效應表示以下事實:由於橫越晶圓表面之不均勻電流密度分佈,晶圓中心中之特徵將以與晶圓邊緣處之特徵不同的(較低)電流密度經金屬電鍍及填充。此可導致不希望的空隙及夾雜物。目前,藉由使用低酸度電鍍液及諸如分流電極(thief
electrode)或分段陽極之工具設計來管理終端效應。一般而言,需要約50ohm/cm2至100ohm/cm2之薄片電阻率,但無硬遮罩之極薄銅晶種可具有明顯高於此之薄片電阻率。
根據本發明之晶種層為銅晶種層或銅合金晶種層。較佳地,根據本發明之晶種層具有小於20nm(例如,範圍在1nm與10nm之間或2nm與5nm之間)之厚度。
根據本發明之硬遮罩可由一或多個層組成。根據本發明之硬遮罩包含至少一個導電的以金屬為主之硬遮罩層以提供所要的較小薄片電阻率。本發明含義內之以金屬為主定義包含金屬之材料。較佳地,根據本發明之至少一個以金屬為主之硬遮罩層與經圖樣化介電基板層直接接觸。用於以金屬為主之硬遮罩層的典型材料包含Co、TaN、Ta、Ti、TiN、Ru、Ir、Au、Rh、Pt、Pd或Ag。此等材料之合金亦為適合的。TaN及TiN為較佳材料,其中TiN尤其較佳。
可利用任何習知沈積製程形成以金屬為主之硬遮罩層,習知沈積製程包括(例如)CVD、PECVD、化學溶液沈積、蒸發、金屬有機沈積、ALD、濺鍍、PVD或電鍍(無電式的或電解的)。金屬層之厚度可取決於所使用的準確金屬界面材料以及用於形成該金屬界面材料之沈積技術而變化。典型地,金屬硬遮罩層具有約2nm至約200nm之厚度,其中約5nm至約100nm之厚度為較佳的,且約10nm至60nm之厚度為尤其較佳的。
金屬硬遮罩可視情況含有包括氧化物、氮化物、環氧氮化物或其組合之額外層(例如,介電層)。適合的介電硬遮罩材料為如SiO2之氧化物或諸如Si3N4之氮化物。利用諸如CVD、PECVD、化學溶液沈積或蒸發之習知沈積製程形成硬遮罩材料。沈積態硬遮罩材料之厚度可取決於所形成之硬遮罩材料之類型、構成硬遮罩材料之層的數目及用於形成該硬遮罩材料之沈積技術而變化。典型地,沈積態硬遮罩材
料具有約2nm至約100nm之厚度,其中約10nm至60nm之厚度為更典型的。
儘管可藉由工具設計減輕電阻率之問題,但在電鍍期間保留金屬硬遮罩之額外益處為減小晶圓之薄層電阻,從而允許更容易地控制電解銅鍍均一性。此為本發明之額外優勢。
在本發明之一個實施例中,硬遮罩在溝槽圖樣之銅填充或障壁/視情況之襯墊/金屬晶種沈積製程之前保持原位。在替代實施例中,在溝槽圖樣之銅填充或障壁/襯墊/金屬晶種沈積製程之前僅部分移除硬遮罩。部分移除可產生更好的晶種覆蓋度,同時保持用於溝槽圖樣之電解銅填充製程之較高總導電率的優勢。若硬遮罩包含一個以上層,則較佳地金屬硬遮罩部分在金屬晶種層之沈積之前保留原位以提供所要的較小電阻率。替代地,取決於溝槽圖樣之特徵大小,可移除硬遮罩之經定義部分。硬遮罩之一部分之移除意謂對應於原始層厚度之(例如)20%、30%或高達60%或70%之層的部分經移除,100%對應於完全移除。
藉由無電式電鍍將銅晶種層沈積至障壁層及/或襯墊層上。倘若無障壁層塗覆至基板材料,則將銅晶種層直接沈積至介電材料上。在後一情況中,沈積銅晶種層包括與充當障壁金屬之第二金屬一起沈積。在塗覆銅晶種層之前沈積至少一個障壁層為較佳的。
「無電式電鍍」意謂「自催化電鍍」。因此,在步驟(ii)中利用之銅鍍浴包含用於Cu(II)離子之還原劑。
在根據本發明之方法中利用的無電式銅鍍浴較佳為水性電鍍浴,亦即溶劑為水。
Cu(II)離子之水溶性來源較佳選自包含硫酸銅、氯化銅、硝酸銅、乙酸銅、甲磺酸銅、氫氧化銅、甲酸銅及其水合物之群。無電式電鍍浴中之Cu(II)離子之濃度較佳在0.05g/l至20g/l,更佳0.1g/l至10
g/l且最佳0.2g/l至6g/l之範圍內。
無電式電鍍浴進一步含有選自包含甲醛、乙醛酸、葡萄糖、蔗糖、纖維素、山梨糖醇、甘露糖醇、葡萄糖酸內酯、次磷酸鹽、硼烷、肼、甲酸、抗壞血酸及其混合物之群的還原劑。還原劑最佳為乙醛酸。還原劑之濃度較佳在0.1g/l至100g/l,更佳0.5g/l至50g/l且最佳1g/l至20g/l之範圍內。
無電式電鍍浴進一步包含Cu(II)離子之至少一種錯合劑,其較佳選自包含羧酸、羥基羧酸、胺基羧酸、烷醇胺、多元醇及其混合物之群。
無電式電鍍浴較佳地保持於15℃至80℃,更佳20℃至60℃且最佳25℃至45℃之範圍內之溫度下。視待沈積銅晶種層之所需厚度及藉由特定電鍍浴組合物獲得的電鍍速率及電鍍參數而定,使基板與無電式電鍍浴接觸5s至30min。
銅晶種層具有甚至(例如)10nm或甚至更小之厚度的均勻厚度分佈。因此,障壁層完全由銅晶種層覆蓋,即使銅晶種層僅具有(例如)10nm或甚至更小之厚度。
基板隨後適於藉由電鍍將金屬沈積至銅晶種層上。
如圖2.3中所展示之藉由電鍍沈積至銅晶種層上之金屬為銅或銅合金。用於將銅或銅合金沈積至銅晶種層上之適合的浴組合物及電鍍條件為此項技術中已知的。
除含有至少一個銅離子源(較佳為具有無機或有機陰離子之銅鹽,例如硫酸銅、甲磺酸銅、焦磷酸銅、氟硼酸銅或胺基磺酸銅)以外,用於銅電沈積之浴額外含有用於增加浴之電導率的至少一種物質,例如硫酸、甲磺酸、焦磷酸、氟硼酸或胺基硫酸。
在一個實施例中,在電解槽中,酸為浴濃度在約50g/l至350g/l,或約180g/l至約280g/l,或約100g/l至約250g/l,或約50g/l至約
90g/l之範圍內之硫酸,銅離子源為浴濃度在約5g/l至約250g/l,或約80g/l至約140g/l,或約180g/l至約220g/l範圍內之五水合硫酸銅。
根據本發明之電鍍浴通常含有至少一種添加劑化合物以用於控制銅層之物理機械特性。適合的添加劑化合物為(例如)聚合含氧化合物、有機硫化合物、硫脲化合物、聚合二甲基苯基吡唑酮化合物(polymeric phenazonium compound)及聚合氮化合物,及任何此等添加劑化合物中之任何兩者或兩者以上之混合物或組合。
對於本發明之電解銅沈積,將電壓施加於基板與陽極之間,電壓經選擇使得電流為0.05安培/dm2(A/dm2)至20A/dm2(在一個實施例中0.2A/dm2至10A/dm2,且在另一實施例中0.5A/dm2至5A/dm2),其中假定電鍍應用於基板之整個表面,將電流表示為(例如)半導體基板表面之安培數/dm2。
在一個實施例中,以脈衝電流或脈衝電壓形式施加電壓。在一個實施例中,以具有雙極性脈衝之反向脈衝形式施加電壓。此等製程為此項技術中所熟知,且在下文更詳細地描述用於本發明之一些實施例的詳細參數。
在一個實施例中,以具有包括正向電流脈衝及反向電流脈衝之雙極性脈衝的反向脈衝形式施加電壓。在一個實施例中,反向電流脈衝之持續時間經調整為約1毫秒至約20毫秒,且在另一實施例中,反向電流脈衝之持續時間經調整為約2毫秒至約10毫秒。在一個實施例中,正向電流脈衝之持續時間經調整為約10毫秒至約200毫秒,且在另一實施例中,正向電流脈衝之持續時間經調整為約20毫秒至約100毫秒。
在一個實施例中,基板表面處之正向電流脈衝的峰值電流密度經調整為約15安培/平方公寸(A/dm2)之最大值,且在另一實施例中,基板表面處之正向電流脈衝的峰值電流密度經調整為約1.5A/dm2至約
8A/dm2之最大值。在一個實施例中,基板表面處之反向電流脈衝的峰值電流密度經調整為約60A/dm2之最大值,且在另一實施例中,基板表面處之反向電流脈衝的峰值電流密度經調整為約30A/dm2至約50A/dm2之最大值。
在一個實施例中,陰極電流脈衝相對於陽極電流脈衝移位。第一電流脈衝與第二電流脈衝之間可包括適合的持續時間之暫停。適合的持續時間可介於約1毫秒至約5毫秒之範圍內,且在一個實施例中約為2毫秒至約4毫秒,且在一個實施例中約為4毫秒。
在電解銅沈積之後,後接其他處理,包括覆蓋層銅、(若存在)視情況之襯墊層、視情況之障壁層及硬遮罩之移除(圖2.4中所展示)。本發明之優勢在於硬遮罩僅需要在銅沈積之後移除。此等方法為此項技術中所熟知。處理包括薄化。薄化可藉由任何已知方法進行。
可根據標準程序移除銅。銅層可簡單地(例如)藉由CMP經移除,或其可經圖樣化以在半導體基板之彼表面上產生電路。
(a)‧‧‧經圖樣化介電基板層
(b)‧‧‧介電層
(c)‧‧‧硬遮罩層
(d)‧‧‧銅晶種/薄銅晶種層
(e)‧‧‧後續電解銅沈積
Claims (16)
- 一種用於將銅電沈積至半導體基板之凹入結構中之方法,其包含以下步驟(i)提供基板,該基板包含至少一個導電特徵、該導電特徵上之至少一個介電層及最外部介電層上之硬遮罩;(ii)在該硬遮罩層及該至少一個介電層中形成凹入結構;(iii)在該所形成之凹入結構的表面上方形成障壁層及視情況形成襯墊層;(iv)藉由濕式化學鍍方法在該障壁層或該視情況之襯墊層上方形成基礎銅晶種層,以為銅或銅合金之後續電解沈積提供充足電導率;(v)將該基板浸入至電解銅鍍系統中之電解銅或銅合金電鍍浴中,其中該基礎金屬晶種層經連接作為陰極,該系統進一步包含銅金屬源及陽極;及在該陽極與該基礎金屬晶種層之間施加電壓,使得電流在其間流動足以使銅填充該等凹入結構之時間;(vi)移除該硬遮罩包括移除沈積至該硬遮罩上之經電沈積之銅。
- 如請求項1之方法,其中該等凹入結構包含均具有5nm至1mm之尺寸的溝槽、盲孔及通孔。
- 如前述請求項中任一項之方法,其中該基礎銅晶種層具有1nm至10nm之厚度。
- 如前述請求項中任一項之方法,其中該半導體基板係選自由以下各者組成之群:矽、二氧化矽及矽基板上之低k介電材料。
- 如前述請求項中任一項之方法,其中該硬遮罩層由一或多個層 組成且包含至少一個基於導電金屬之硬遮罩層。
- 如請求項5之方法,其中該基於導電金屬之硬遮罩層係選自Co、TaN、Ta、Ti、TiN、Ru、Ir、Au、Rh、Pt、Pd及Ag。
- 如前述請求項中任一項之方法,其中移除該硬遮罩層之該步驟包括化學機械拋光及/或蝕刻。
- 如前述請求項中任一項之方法,其中根據步驟(iv)提供基礎銅晶種層之該濕式化學鍍方法為水性銅鍍方法。
- 如請求項8之方法,其中該水性銅鍍方法包含以下步驟:使該介電基板與水性無電式銅鍍浴接觸,該水性無電式銅鍍浴包含a. Cu(II)離子之水溶性來源,b. Cu(II)離子之還原劑,c. Cu(II)離子之至少一種錯合劑。
- 如請求項9之方法,其中該無電式銅鍍浴中之該還原劑係選自由以下各者組成之群:甲醛、乙醛酸、葡萄糖、蔗糖、纖維素、山梨糖醇、甘露糖醇、葡萄糖酸內酯、次磷酸鹽、硼烷、肼、甲酸、抗壞血酸及其混合物。
- 如請求項9及10之方法,其中該無電式銅鍍浴中之Cu(II)離子之該錯合劑係選自由以下各者組成之群:羧酸、羥基羧酸、胺基羧酸、烷醇胺、多元醇及其混合物。
- 如請求項9至11之方法,其中Cu(II)離子之該水溶性來源係選自包含以下各者之群:硫酸銅、氯化銅、硝酸銅、乙酸銅、甲磺酸銅、氫氧化銅、甲酸銅及其水合物。
- 如前述請求項中任一項之方法,其中根據步驟(v)之該電解銅鍍浴包含濃度在50g/l至350g/l之範圍內之硫酸、產生約5g/l至約250g/l範圍內之銅離子濃度之銅離子來源,及用於控制該經沈積 銅之物理機械特性之至少一種添加劑,該添加劑包含聚合含氧化合物、有機硫化合物、硫脲化合物及聚合二甲基苯基吡唑酮化合物(polymeric phenazonium compound)中之一或多者。
- 如前述請求項中任一項之方法,其中以脈衝電流或脈衝電壓形式施加該電壓。
- 如請求項14之方法,其中以具有包括正向電流脈衝及反向電流脈衝之雙極性脈衝的反向脈衝形式施加該電壓。
- 如請求項14或15之方法,其中該反向電流脈衝之持續時間經調整為1毫秒至20毫秒,且其中該正向電流脈衝之持續時間經調整為10毫秒至200毫秒。
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EP14199374.1A EP3034655A1 (en) | 2014-12-19 | 2014-12-19 | Trench pattern wet chemical copper metal filling using a hard mask structure |
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CA2883408C (en) | 2012-09-04 | 2021-08-31 | Modernfold Inc. | Panel seal systems |
US10103056B2 (en) * | 2017-03-08 | 2018-10-16 | Lam Research Corporation | Methods for wet metal seed deposition for bottom up gapfill of features |
WO2019066855A1 (en) | 2017-09-28 | 2019-04-04 | Intel Corporation | INTERCONNECTIONS HAVING A PORTION WITHOUT COATING MATERIAL AND RELATED STRUCTURES, DEVICES AND METHODS |
EP4018790A1 (en) * | 2019-08-19 | 2022-06-29 | Atotech Deutschland GmbH & Co. KG | Manufacturing sequences for high density interconnect printed circuit boards and a high density interconnect printed circuit board |
CN116682785B (zh) * | 2023-08-03 | 2023-12-29 | 上海电子信息职业技术学院 | 一种采用葡萄糖实现tsv完全填充方法 |
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US7528066B2 (en) * | 2006-03-01 | 2009-05-05 | International Business Machines Corporation | Structure and method for metal integration |
US7396768B2 (en) * | 2006-10-20 | 2008-07-08 | Hitachi Global Storage Technologies Netherlands B.V. | Copper damascene chemical mechanical polishing (CMP) for thin film head writer fabrication |
DE102007020269A1 (de) * | 2007-04-30 | 2008-11-06 | Advanced Micro Devices, Inc., Sunnyvale | Halbleiterstruktur mit einer elektrischen Verbindung und Verfahren zu ihrer Herstellung |
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