JP6832067B2 - シリコン貫通ビア内への銅の電着のための、ニッケルライナおよびコバルトライナの前処理 - Google Patents
シリコン貫通ビア内への銅の電着のための、ニッケルライナおよびコバルトライナの前処理 Download PDFInfo
- Publication number
- JP6832067B2 JP6832067B2 JP2016034972A JP2016034972A JP6832067B2 JP 6832067 B2 JP6832067 B2 JP 6832067B2 JP 2016034972 A JP2016034972 A JP 2016034972A JP 2016034972 A JP2016034972 A JP 2016034972A JP 6832067 B2 JP6832067 B2 JP 6832067B2
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- Prior art keywords
- electroplating
- wet
- copper
- solution
- wafer substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 123
- 239000010949 copper Substances 0.000 title claims description 114
- 229910052802 copper Inorganic materials 0.000 title claims description 104
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 101
- 229910052759 nickel Inorganic materials 0.000 title claims description 62
- 229910017052 cobalt Inorganic materials 0.000 title claims description 35
- 239000010941 cobalt Substances 0.000 title claims description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 14
- 229910052710 silicon Inorganic materials 0.000 title claims description 14
- 239000010703 silicon Substances 0.000 title claims description 14
- 238000004070 electrodeposition Methods 0.000 title claims description 12
- 230000000149 penetrating effect Effects 0.000 title claims description 3
- 238000009713 electroplating Methods 0.000 claims description 162
- 238000000034 method Methods 0.000 claims description 145
- 239000000758 substrate Substances 0.000 claims description 133
- 238000007747 plating Methods 0.000 claims description 73
- 239000003112 inhibitor Substances 0.000 claims description 71
- 150000002500 ions Chemical class 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 44
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910001431 copper ion Inorganic materials 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 16
- 229920002120 photoresistant polymer Polymers 0.000 claims description 15
- 125000003827 glycol group Chemical group 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- 238000007872 degassing Methods 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 239000002659 electrodeposit Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 166
- 239000000243 solution Substances 0.000 description 165
- 235000012431 wafers Nutrition 0.000 description 125
- 230000008569 process Effects 0.000 description 40
- 229910052751 metal Inorganic materials 0.000 description 24
- 239000002184 metal Substances 0.000 description 24
- 238000012545 processing Methods 0.000 description 22
- 239000003792 electrolyte Substances 0.000 description 19
- 239000004065 semiconductor Substances 0.000 description 19
- 230000007797 corrosion Effects 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 18
- 238000009792 diffusion process Methods 0.000 description 17
- 238000000151 deposition Methods 0.000 description 16
- 230000004888 barrier function Effects 0.000 description 15
- 230000008021 deposition Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000005240 physical vapour deposition Methods 0.000 description 12
- 239000012530 fluid Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- -1 alkylene glycols Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 238000000231 atomic layer deposition Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005341 cation exchange Methods 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
- 238000004140 cleaning Methods 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 2
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 2
- 238000005323 electroforming Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XXACTDWGHQXLGW-UHFFFAOYSA-M Janus Green B chloride Chemical compound [Cl-].C12=CC(N(CC)CC)=CC=C2N=C2C=CC(\N=N\C=3C=CC(=CC=3)N(C)C)=CC2=[N+]1C1=CC=CC=C1 XXACTDWGHQXLGW-UHFFFAOYSA-M 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical compound [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RYGMFSIKBFXOCR-AHCXROLUSA-N copper-60 Chemical compound [60Cu] RYGMFSIKBFXOCR-AHCXROLUSA-N 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000370 mercury sulfate Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000013515 script Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 238000010005 wet pre-treatment Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/001—Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells
-
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
-
- 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
- H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
-
- 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
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
-
- 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
-
- 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
- H01L21/76879—Filling of holes, grooves or trenches, e.g. vias, with conductive material by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Description
例1(比較例):60μmの深さと、開口における6μmの直径とを有する複数のビアを含有するウエハ基板が使用された。基板は、無電解蒸着によって、WN/W拡散障壁二重層上にNiBシード層を蒸着された。基板は、ウェット層を形成するために、大気圧未満の圧力下において、脱気された脱イオン水を吹き付けられた。圧力は、次いで、大気圧まで引き上げられ、基板は、プリウェットチャンバから電気めっきセルに移送され、そこで、凹部特徴を充填するために、60g/Lの銅イオンと、60g/LのH2SO4と、50ppmの塩素イオンと、MLI HSL−A/B/C促進剤と、抑制剤と、レベラ(ワシントン州モーゼスレイクのMoses Lake Industriesから入手可能)とを含有する酸性めっき溶液を使用して、銅を電着された。充填されたビアの断面の走査型電子顕微鏡(SEM)画像において、空隙が観察された。空隙は、ウエハの中心部分および中間部分に位置するビアの底部に観察された。ウエハの縁に位置するビアには、空隙は観察されなかった。
ニッケル層およびコバルト層の不動態化のためには、プリウェット液内に第二銅イオンを使用することが好ましいが、プリウェット液内の第二銅イオンは、このような不動態化が可能である任意の酸化剤によって置き換え可能である。酸化剤の例には、第二鉄イオン、クロム酸イオン、および硝酸イオンがある。
本発明は、たとえば、以下のような態様で実現することもできる。
適用例1:
1つ以上の凹部特徴を含むウエハ基板上に銅を電気めっきする方法であって、
(a)その表面の少なくとも一部分の上にニッケル含有シード層および/またはコバルト含有シード層が露出されたウエハ基板を用意することと、
(b)前記ウエハ基板上の前記シード層をプリウェットするために、少なくとも約10g/Lの濃度の第二銅(Cu 2+ )イオンと、電気めっき抑制剤とを含むプリウェット液に前記ウエハ基板を接触させることと、
(c)前記シード層の上に銅を電着させることであって、前記電着された銅は、前記1つ以上の凹部特徴を少なくとも部分的に充填する、ことと、
を備える方法。
適用例2:
適用例1の方法であって、
前記シード層は、ニッケル含有層である、方法。
適用例3:
適用例1の方法であって、
(c)は、酸性の電気めっき溶液を使用して前記シード層上に銅を電着させることを含む、方法。
適用例4:
適用例1の方法であって、
前記ウエハ基板は、(b)において、大気圧未満の圧力下において前記プリウェット液に接触される、方法。
適用例5:
適用例2の方法であって、
前記プリウェット液は、少なくとも約30g/Lの濃度で第二銅(Cu 2+ )イオンを含む、方法。
適用例6:
適用例2の方法であって、
前記電気めっき抑制剤の濃度は、少なくとも約50ppmである、方法。
適用例7:
適用例2の方法であって、
前記電気めっき抑制剤は、ポリアルキレングリコール群からの化合物である、方法。
適用例8:
適用例2の方法であって、
前記電気めっき抑制剤は、アミノ基を含有するポリアルキレングリコール群からの化合物である、方法。
適用例9:
適用例2の方法であって、
前記プリウェット液のpHは、約2未満である、方法。
適用例10:
適用例2の方法であって、さらに、
前記プリウェット液を、前記ウエハ基板に接触させる前に脱気することを備える方法。
適用例11:
適用例2の方法であって、
前記プリウェット液内の第二銅イオンの濃度は、(c)において銅を電気めっきするために使用される電気めっき溶液内の第二銅イオンの濃度と同じであるまたはそれよりも大きい、方法。
適用例12:
適用例2の方法であって、
前記プリウェット液は、(c)において銅を電気めっきするために使用される電気めっき溶液と同じ組成を有する、方法。
適用例13:
適用例2の方法であって、
前記プリウェット液は、さらに、ハロゲン化物、電気めっき促進剤、電気めっきレベラ、およびこれらの組み合わせからなる群より選択される添加剤を含む、方法。
適用例14:
適用例2の方法であって、
前記プリウェット液は、硫酸、メタンスルホン酸、およびこれらの組み合わせからなる群より選択される酸を含む、方法。
適用例15:
適用例2の方法であって、
前記ニッケル含有層は、NiB層である方法。
適用例16:
適用例2の方法であって、
前記ニッケル含有層は、NiP層である方法。
適用例17:
適用例2の方法であって、
前記1つ以上の凹部特徴は、シリコン貫通ビア(TSV)である、方法。
適用例18:
適用例2の方法であって、
前記プリウェット液は、酸と、少なくとも約30g/Lの濃度の第二銅イオンと、少なくとも約50ppmの濃度の電気めっき抑制剤とを含み、前記電気めっき抑制剤は、ポリアルキレングリコール群からの化合物である、方法。
適用例19:
適用例1の方法であって、さらに、
前記ウエハ基板にフォトレジストを塗布することと、
前記フォトレジストを露光することと、
前記フォトレジストをパターン形成し、前記パターンを前記ウエハ基板に転写することと、
前記ウエハ基板から前記フォトレジストを選択的に除去することと、
を備える方法。
適用例20:
1つ以上の凹部特徴を含むウエハ基板上の露出したニッケル含有シード層および/またはコバルト含有シードの上に銅を電気めっきするための装置であって、
(a)前記ウエハ基板上にプリウェット液を供給するように構成されたプリウェットチャンバと、
(b)銅電気めっき溶液を保持するように構成されためっき容器であって、前記装置は、前記電気めっき溶液からの銅を前記ウエハ基板上の前記シード層上に電着させるように構成される、めっき容器と、
(c)
(i)前記ウエハ基板上の前記シード層をプリウェットするために、少なくとも約10g/Lの濃度の第二銅(Cu 2+ )イオンと、電気めっき抑制剤とを含むプリウェット液に、前記ウエハ基板を接触させるためのプログラム命令および/またはロジックと、
(ii)前記シード層の上に銅を電着させるためのプログラム命令および/またはロジックであって、前記電着された銅は、前記1つ以上の凹部特徴を少なくとも部分的に充填する、プログラム命令および/またはロジックと、
を含むコントローラと、
を備える装置。
Claims (28)
- 1つ以上の凹部特徴を含むウエハ基板上に銅を電気めっきする方法であって、
(a)その表面の少なくとも一部分の上にニッケル含有シード層および/またはコバルト含有シード層が露出されたウエハ基板を用意することと、
(b)前記ウエハ基板に電気的にバイアスをかけることなく、前記ウエハ基板上の前記シード層をプリウェットするために、少なくとも10g/Lの濃度の第二銅(Cu2+)イオンと、電気めっき抑制剤とを含むプリウェット液に前記ウエハ基板を接触させることと、
(c)酸性の電気めっき溶液を使用して前記シード層の上に銅を電着させることであって、前記電着された銅は、前記1つ以上の凹部特徴を少なくとも部分的に充填する、ことと、
を備える方法。 - 請求項1に記載の方法であって、
前記シード層は、ニッケル含有層である、方法。 - 請求項1に記載の方法であって、
前記ウエハ基板は、(b)において、大気圧未満の圧力下において前記プリウェット液に接触される、方法。 - 請求項2に記載の方法であって、
前記プリウェット液は、少なくとも30g/Lの濃度で第二銅(Cu2+)イオンを含む、方法。 - 請求項2に記載の方法であって、
前記電気めっき抑制剤の濃度は、少なくとも50ppmである、方法。 - 請求項2に記載の方法であって、
前記電気めっき抑制剤は、ポリアルキレングリコール群からの化合物である、方法。 - 請求項2に記載の方法であって、
前記電気めっき抑制剤は、アミノ基を含有するポリアルキレングリコール群からの化合物である、方法。 - 請求項2に記載の方法であって、
前記プリウェット液のpHは、2未満である、方法。 - 請求項2に記載の方法であって、さらに、
前記プリウェット液を、前記ウエハ基板に接触させる前に脱気することを備える方法。 - 請求項2に記載の方法であって、
前記プリウェット液内の第二銅イオンの濃度は、(c)において銅を電気めっきするために使用される電気めっき溶液内の第二銅イオンの濃度と同じであるまたはそれよりも大きい、方法。 - 請求項2に記載の方法であって、
前記プリウェット液は、(c)において銅を電気めっきするために使用される電気めっき溶液と同じ組成を有する、方法。 - 請求項2に記載の方法であって、
前記プリウェット液は、さらに、ハロゲン化物、電気めっき促進剤、電気めっきレベラ、およびこれらの組み合わせからなる群より選択される添加剤を含む、方法。 - 請求項2に記載の方法であって、
前記プリウェット液は、硫酸、メタンスルホン酸、およびこれらの組み合わせからなる群より選択される酸を含む、方法。 - 請求項2に記載の方法であって、
前記ニッケル含有層は、NiB層である方法。 - 請求項2に記載の方法であって、
前記ニッケル含有層は、NiP層である方法。 - 請求項2に記載の方法であって、
前記1つ以上の凹部特徴は、シリコン貫通ビア(TSV)である、方法。 - 請求項2に記載の方法であって、
前記プリウェット液は、酸と、少なくとも30g/Lの濃度の第二銅イオンと、少なくとも50ppmの濃度の電気めっき抑制剤とを含み、前記電気めっき抑制剤は、ポリアルキレングリコール群からの化合物である、方法。 - 請求項1に記載の方法であって、さらに、
前記ウエハ基板にフォトレジストを塗布することと、
前記フォトレジストを露光することと、
前記フォトレジストをパターン形成し、前記パターンを前記ウエハ基板に転写することと、
前記ウエハ基板から前記フォトレジストを選択的に除去することと、
を備える方法。 - 1つ以上の凹部特徴を含むウエハ基板上の露出したニッケル含有シード層および/またはコバルト含有シード層の上に銅を電気めっきするための装置であって、
(a)前記ウエハ基板上にプリウェット液を供給するように構成されたプリウェットチャンバと、
(b)銅電気めっき溶液を保持するように構成されためっき容器であって、前記装置は、前記銅電気めっき溶液からの銅を前記ウエハ基板上の前記シード層上に電着させるように構成される、めっき容器と、
(c)コントローラであって、
(i)前記ウエハ基板に電気的にバイアスをかけることなく、前記ウエハ基板上の前記シード層をプリウェットするための、少なくとも10g/Lの濃度の第二銅(Cu2+)イオンと、電気めっき抑制剤とを含むプリウェット液への、前記ウエハ基板の接触を起こさせるためのプログラム命令および/またはロジックと、
(ii)酸性の電気めっき溶液を使用して前記シード層の上への銅の電着を起こさせるためのプログラム命令および/またはロジックであって、前記電着された銅は、前記1つ以上の凹部特徴を少なくとも部分的に充填する、プログラム命令および/またはロジックと、
を含むコントローラと、
を備える装置。 - 請求項19に記載の装置であって、
(i)において、前記電気めっき抑制剤の濃度は、少なくとも50ppmである、装置。 - 請求項19に記載の装置であって、
前記コントローラは、さらに、大気圧未満の圧力下で(i)の前記プリウェットを行わせるためのプログラム命令および/またはロジックを含む、装置。 - 請求項19に記載の装置であって、
(i)において、前記銅イオンの前記濃度は、少なくとも30g/Lである、装置。 - 請求項19に記載の装置であって、
(i)において、前記抑制剤は、ポリエチレングリコール群からの化合物である、装置。 - 請求項19に記載の装置であって、
(i)において、前記プリウェット液のpHは、2未満である、装置。 - 請求項19に記載の装置であって、
前記コントローラは、さらに、プリウェット前に、前記プリウェット液の脱気を行わせるためのプログラム命令および/またはロジックを含む、装置。 - 請求項19に記載の装置であって、
前記プリウェットチャンバは、前記プリウェット液を前記ウエハ基板上に吹き付けるまたは流すように構成される、装置。 - 請求項19に記載の装置であって、
前記プリウェットチャンバは、前記ウエハ基板を前記プリウェット液に浸漬するように構成される、装置。 - 請求項19に記載の装置であって、
前記プリウェットチャンバおよび前記めっき容器は、1つのモジュール内に含まれる、装置。
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TWI769131B (zh) | 2022-07-01 |
KR102509652B1 (ko) | 2023-03-13 |
TW201708622A (zh) | 2017-03-01 |
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