TW200907113A - Codeposition of copper nanoparticles in through silicon via filling - Google Patents
Codeposition of copper nanoparticles in through silicon via filling Download PDFInfo
- Publication number
- TW200907113A TW200907113A TW097123101A TW97123101A TW200907113A TW 200907113 A TW200907113 A TW 200907113A TW 097123101 A TW097123101 A TW 097123101A TW 97123101 A TW97123101 A TW 97123101A TW 200907113 A TW200907113 A TW 200907113A
- Authority
- TW
- Taiwan
- Prior art keywords
- copper
- reaction product
- vinylpyridine
- composition
- electrolytic
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 191
- 239000010949 copper Substances 0.000 title claims abstract description 191
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 95
- 238000011049 filling Methods 0.000 title description 2
- 229910052710 silicon Inorganic materials 0.000 title 1
- 239000010703 silicon Substances 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 238000007747 plating Methods 0.000 claims abstract description 34
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 23
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 58
- 238000009713 electroplating Methods 0.000 claims description 38
- 230000001588 bifunctional effect Effects 0.000 claims description 37
- 239000007795 chemical reaction product Substances 0.000 claims description 37
- 150000001412 amines Chemical class 0.000 claims description 30
- 239000003112 inhibitor Substances 0.000 claims description 29
- -1 fluorenyl monomethyl hydrazine Chemical compound 0.000 claims description 25
- 238000000151 deposition Methods 0.000 claims description 24
- 229920001400 block copolymer Polymers 0.000 claims description 21
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003760 tallow Substances 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002103 nanocoating Substances 0.000 claims description 6
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 claims description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 5
- 229940073608 benzyl chloride Drugs 0.000 claims description 5
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- BIAAQBNMRITRDV-UHFFFAOYSA-N 1-(chloromethoxy)-2-methoxyethane Chemical compound COCCOCCl BIAAQBNMRITRDV-UHFFFAOYSA-N 0.000 claims description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims description 2
- WZIYCIBURCPKAR-UHFFFAOYSA-N 4-(chloromethyl)pyridine Chemical compound ClCC1=CC=NC=C1 WZIYCIBURCPKAR-UHFFFAOYSA-N 0.000 claims description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- BUOSLGZEBFSUDD-BGPZCGNYSA-N bis[(1s,3s,4r,5r)-4-methoxycarbonyl-8-methyl-8-azabicyclo[3.2.1]octan-3-yl] 2,4-diphenylcyclobutane-1,3-dicarboxylate Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1C(C=2C=CC=CC=2)C(C(=O)O[C@@H]2[C@@H]([C@H]3CC[C@H](N3C)C2)C(=O)OC)C1C1=CC=CC=C1 BUOSLGZEBFSUDD-BGPZCGNYSA-N 0.000 claims description 2
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 claims description 2
- 229940117583 cocamine Drugs 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 150000002430 hydrocarbons Chemical group 0.000 claims 3
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- 150000004702 methyl esters Chemical class 0.000 claims 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 claims 1
- 229960001950 benzethonium chloride Drugs 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 238000005363 electrowinning Methods 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002466 imines Chemical class 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 229920002359 Tetronic® Polymers 0.000 description 25
- 239000000243 solution Substances 0.000 description 22
- 239000000654 additive Substances 0.000 description 19
- 238000001465 metallisation Methods 0.000 description 19
- 235000012431 wafers Nutrition 0.000 description 19
- 230000008021 deposition Effects 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000006255 coating slurry Substances 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920005682 EO-PO block copolymer Polymers 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006295 polythiol Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- RRJHFUHAKCSNRY-UHFFFAOYSA-L [Cu+2].[O-]P([O-])=O Chemical compound [Cu+2].[O-]P([O-])=O RRJHFUHAKCSNRY-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 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
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 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
- 238000009792 diffusion process Methods 0.000 description 1
- WIYCQLLGDNXIBA-UHFFFAOYSA-L disodium;3-(3-sulfonatopropyldisulfanyl)propane-1-sulfonate Chemical group [Na+].[Na+].[O-]S(=O)(=O)CCCSSCCCS([O-])(=O)=O WIYCQLLGDNXIBA-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical class CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XTPRURKTXNFVQT-UHFFFAOYSA-N hexyl(trimethyl)azanium Chemical compound CCCCCC[N+](C)(C)C XTPRURKTXNFVQT-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
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
- H01L21/70—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
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
-
- 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
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
200907113 九、發明說明 【發明之技術領域】 本發明一般係關於使用銅金屬化之通孔塡充技術且特 別是關於使用銅奈米粒子之直通矽通孔的通孔塡充技術。 【先前技術】 積體電路（1C )裝置含有在互連結構之各層間形成電 連接之通孔。在一型式中’通孔可以從1 c鑄模後側延伸 至前方（鑄模之活性側）。此型式之通孔構造在此技藝中 已知爲“直通矽通孔”（TSV)。在某些裝置中，直通矽通 孔可以在晶片疊層物中之一對黏合的晶片間形成互連。 TSV之深度是晶片厚度之函數’其可以是約30微米 至約5 0 0微米，例如約2 5 0微米。在現有技藝狀態中，在 TSV中通孔開口具有例如約1微米至約200微米，例如介 於約1 〇微米及約5 0微米間之直徑的入口尺寸。 電解銅金屬化慣常用在半導體積體電路（1C)裝置製 造中以提供電互連。慣常之電解銅澱積浴最短可以花費半 小時且最常可以花費20小時以塡充直通矽通孔。後者爲 在商業適用性方面上的主要阻礙。因此，在此技藝中需要 更快之使含TSV之裝置的銅金屬化的方法。 【發明內容】 發明總論 因此本發明目的是要提供一種用於TSV之電解銅塡充 200907113 方法，此方法是經濟的且達成高品質的塡充。 因此簡明地，本發明係關於一種在半導體積體電路基 板中使通孔特徵金屬化所用之電解銅電鍍組成物。該組成 物包含經塗覆之銅奈米粒子’此粒子包含銅奈米粒子及雙 官能性分子塗層，其中至少約9 0 %銅奈米粒子具有至少一 個少於約5 00奈米之橫向尺寸’及至少約90%銅奈米粒子 具有至少一個大於約5奈米之橫向尺寸。 本發明另外關於一種用於電解澱積銅於半導體積體電 路裝置基板中之方法，該基板包含具有底部、側壁、和頂 部開口之通孔特徵，而該頂部開口具有至少1微米之入口 尺寸。該方法包含將半導體積體電路裝置基板浸入包含經 塗覆之銅奈米粒子之電解電鍍組成物中，而該經塗覆之銅 奈米粒子包含銅奈米粒子及雙官能性分子塗層，其中至少 約9 0 %銅奈米粒子具有至少一個少於約5 0 0奈米之橫向尺 寸，且至少約90%銅奈米粒子具有至少一個大於約5奈米 之橫向尺寸；及將電流供應至電解組成物以令銅澱積在基 板上及通孔特徵中。 其他目的及特徵部分是明顯的且部分在下文中指出。 本發明之具體表現的詳細描述 本發明係關於一種在半導體積體電路裝置製造中通孔 金屬化之方法。本發明方法特別有用於無缺陷通孔超塡充 方法中以商業上可實施之比率塡充直通矽通孔。“無缺陷” 通孔超塡充方法的特徵在於良好之晶種層覆蓋，電解溶液 -6- 200907113 向下適當地潤濕通孔底部，抑制劑/均平劑及加速劑作用 間之可接受的平衡以達成快速之底部向上的塡充’及合適 之質量傳遞。此種方法達成完全金屬化的通孔。參見圖 1 A。由不完美之方法所得之缺陷包括接縫（參見圖1 B ) 及空隙（參見圖1C)。整合（conformal )塡充經常發生 接縫，此常因電解溶液中不合適之加速劑及/或澱積方法 使用不正確之波形。因箍斷發生空隙’此常因抑制劑/均 平劑及加速劑作用間之非最佳平衡及不正確之波形之使用 〇 本發明之一方面係關於用於TSV塡充之包含銅粒子之 電解銅澱積浴。特別地，電解銅澱積浴包含具有至少一個 奈米等級的橫向尺寸之銅粒子。這些銅粒子在本文中稱爲 銅奈米粒子。本發明之電解銅電鍍組成物可以包含銅奈米 粒子源及銅離子源。較佳地’銅奈米粒子及銅離子源的用 量係經塗覆之銅奈米粒子濃度（單位是銅奈米粒子之克數 /升）對銅離子濃度（單位是克/升）的比例約0·00 5至 約0.4間，較佳在約0.01至約〇·2間。換言之’銅離子濃 度（單位是克/升）典型是經塗覆之銅奈米粒子濃度（單 位是克/升）的5至100倍。 銅奈米粒子係指銅粒子，其中至少約90°/。粒子具有至 少一個少於500奈米（“nm”）之橫向尺寸’且至少約90% 粒子具有至少一個大於5奈米之橫向尺寸’較佳地至少約 9 0 %粒子具有至少一個少於5 0 〇奈米之橫向尺寸’且至少 約90 %粒子具有至少一個大於20奈米之橫向尺寸。甚至 200907113 更佳地，用於本發明之方法中的銅粒子之粒子尺寸分布爲 其中至少約9 0 %粒子具有至少一個少於2 5 0奈米之橫向尺 寸，且至少約90%粒子具有至少一個大於100奈米之橫向 尺寸。在一較佳具體表現中，至少90%粒子的特徵在於此 種粒子之所有橫向尺寸皆少於500奈米。本文中所有百分 比係按重量計，除非另有陳述。 可得呈多種形狀之銅奈米粒子，例如球形、扁橢圓體 、扁長橢圓體、小板、薄片、錐體、桶狀物、及棒狀物。 關於球形銅奈米粒子，奈米粒子通常是不規則形狀之球體 (亦即包含使其形狀與完美球形有偏差之草皮狀物、凸起 物等）。關於不規則球形銅奈米粒子，該至少一個奈米等 級的橫向尺寸實質是奈米粒子之直徑。 形狀大略呈扁橢圓體之銅奈米粒子可以藉三個垂直的 橫向尺寸、二個半-主軸及一個半-次軸來定義，且至少約 90%扁粒子具有至少一個少於500奈米之橫向尺寸，且至 少約90%扁粒子具有至少一個大於5奈米之橫向尺寸’較 佳地至少約9 0 %扁粒子具有至少一個少於5 0 0奈米之橫向 尺寸，且至少約90%扁粒子具有至少一個大於20奈米之 橫向尺寸。較佳地，至少90 %扁粒子之全部三個橫向尺寸 在約2 0奈米及約5 0 0奈米間，甚至更佳地全部三個橫向 尺寸在約100奈米及約250奈米間。 形狀約呈扁長橢圓體之銅奈米粒子也藉三個垂直橫向 尺寸、一個半-主軸及二個半-次軸所定義，且至少約9 0 % 扁長粒子具有至少一個少於5 00奈米之橫向尺寸’且至少 200907113 約9 0%扁長粒子具有至少一個大於5奈米之橫向尺寸，較 佳地至少約9 0 %扁長粒子具有至少一個少於5 0 0奈米之橫 向尺寸，且至少約90 %扁長粒子具有至少一個大於20奈 米之橫向尺寸。較佳地，至少9 0 %扁長球體之全部三個橫 向尺寸在約2 0奈米及約5 0 0奈米間’甚至更佳地全部三 個橫向尺寸在約1〇〇奈米及約25 0奈米間。 小板、桶狀物、棒狀物、錐體及薄片也可鑒於橫向尺 寸來定義。關於這些形狀之每一者，至少約90%粒子具有 至少一個少於500奈米之橫向尺寸，且至少約90%粒子具 有至少一個大於5奈米之橫向尺寸；較佳地，至少約9 0 % 粒子具有至少一個少於5 0 0奈米之橫向尺寸’且至少約 90 %粒子具有至少一個大於20奈米之橫向尺寸；甚至更佳 地，至少約9 0 %粒子具有至少一個少於2 5 0奈米之橫向尺 寸，且至少約90%粒子具有至少一個大於100奈米之橫向 尺寸。較佳地，奈米粒子形狀之每一者的每一橫向尺寸是 少於5 00奈米且大於20奈米。 在一較佳具體表現中，銅奈米粒子是不規則形狀之球 體，其中至少90%粒子具有少於5 00奈米之直徑，且至少 約90%粒子具有大於20奈米之直徑；較佳地，至少約 9 0 %粒子具有少於2 5 0奈米之直徑，且至少9 0 %粒子具有 大於100奈米之直徑。 在粒子尺寸分布範圍內可得銅奈米粒子，且供特別應 用之粒子尺寸分布的選擇是依照欲被金屬化之通孔的尺寸 而定。爲塡充具有較大開口直徑的通孔以確保商業上可實 -9- 200907113 施之塡充比率，較大之粒子是較佳的；然而’爲塡充具有 較小開口直徑之通孔以確保無空隙塡充’較小之粒子是較 佳的。爲塡充具有較小開口直徑（例如低於約1 〇微米） 之通孔’可以選擇之銅奈米粒子是其中至少約8 〇 °/°粒子具 有至少一個在約20至約50奈米間之尺寸者。爲塡充具有 較大開口直徑（例如高於約1 0微米）之通孔’可以選擇 之銅奈米粒子是其中至少90 %粒子具有至少一個在約50 奈米至約300奈米間之尺寸者。已發現：奈米粒子藉由作 爲晶種粒子（其周圍可以形成銅電鍍物）及於澱積金屬化 中作爲塡料粒子而使澱積速率加速。在二方面’相較於慣 用之使用電解電鍍浴（其中澱積金屬源由銅原子組成）的 金屬化，銅奈米粒子增加塡充速率。另外’本發明之銅澱 積方法實質產生無空隙且無缺陷之金屬化通孔。 在本發明方法中可用之銅奈米粒子可從很多來源獲得 。可應用之來源包括ND C0PPer p〇wder C1_250 (具有約 250奈米之平均直徑的銅球體）及ND Copper Powder Cl-500 (具有約500奈米之平均直徑的銅球體）（二者可從 NanoDynamics ( Buffalo, NY)獲得），及 Copper Powder 20-9008 (其也可從 NanoDynamics 獲得）。 銅奈米粒子可在添加至電解銅澱積浴前被製備。奈米 粒子製備可包含清潔粒子以除去表面氧化物；及在表面活 性劑溶液中處理粒子以使粒子可分散於水溶液中。適於除 去表面氧化物之清潔用溶液較佳是強酸性，且可以包含有 機酸及無機酸。較佳地，清潔用溶液之酸鹼値在約1.4至 -10- 200907113 約3.4間，例如在約1 . 8至約3間，例如約2.4。可應用之 無機酸包括礦物酸例如氫氟酸、磷酸及氫氯酸。應避免使 用強氧化性無機酸例如硝酸。清潔用溶液中所包括之可應 用之有機酸包括乙酸、三氯乙酸及三氟乙酸。在一具體表 現中，銅奈米粒子用包含濃縮之乙酸及氫氟酸（5%)之溶 液來清潔以除去表面氧化物。粒子可以藉浸漬粒子於清潔 用溶液或藉噴灑而清潔。清潔典型進行約1分鐘至約5分 鐘以確保適當的除去表面氧化物。超過5分鐘之清洗不能 提供進一步之清潔。清潔用溶液之溫度可以在約1 8 °C至約 2 5 °C間。粒子在清潔後並不洗濯以避免表面再次氧化。 在清潔後，銅奈米粒子被塗覆雙官能性分子。雙官能 性分子包含疏水性基團及親水性基團。在於包含雙官能性 分子之溶液中塗覆奈米粒子的期間，疏水性基團與銅奈米 粒子有交互作用；但親水性基團與水溶液（典型是含有例 如有機添加劑之銅-硫酸電解溶液）有交互作用。藉著與 銅離子有此種方式的交互作用，雙官能性分子使銅奈米粒 子可分散於水溶液中，例如在銅奈米粒子周圍形成雙官能 性分子之微胞塗層。另外，因爲奈米粒子類似地被充電（ 例如在較佳具體表現中係被正充電），雙官能性塗層抑制 銅奈米粒子之附聚。因此，在溶液中銅奈米粒子之粒子尺 寸分布保持與乾燥之銅奈米粒子之粒子尺寸分布實質相同 ，除了因雙官能性塗層而使粒子尺寸稍微增加。 雙官能性分子可以是中性的或正充電的。較佳地’雙 官能性分子之數目具有總正電荷以使經塗覆之銅奈米粒子 -11 - 200907113 負載總正電荷。正電荷是想要的，因爲包含直通矽通孔之 晶片基板係在電解銅澱積期間作爲陰極（充負電的電極） 。因此，當整流器（亦即電力供應器）打開時，經塗覆之 銅奈米粒子被靜電地或電動力地引流至晶片表面。 在一具體表現中，作爲塗層材料之雙官能性分子包含 胺及至少一疏水性長鏈烴基。胺部分代表親水性首基且在 酸性溶液中會變爲陽離子性（一級、二級、三級胺）或爲 永久陽離子性（四級胺）。較佳地，胺是四級胺。長鏈烴 基代表疏水性尾基。烴基可以是約6至約24個碳長度。 烴基較佳是至少6個碳長度以有足夠疏水性以在銅奈米粒 子周圍形成微胞塗層。烴鏈較佳不多於約24個碳長度以 確保恰當之溶解性。較佳地，烴鏈比6個碳原子更長且比 24個碳原子更短，例如在約8個碳原子及約16個碳原子 間，更佳是在約1 〇個碳原子及約1 4個碳原子間。例示之 包含胺及烴基之雙官能性分子包括氯化十二烷基三甲基銨 (例如得自AkzoNobel之Arquad 12-35W)，氯化十二烷 基二甲基苄基銨；氯化十六烷基三甲基銨（例如 Arquadl6-29及Arquadl6-29);氯化十八烷基三甲基銨； 氯化十八烷基二甲基苄基銨；氯化牛脂苄基二甲基銨、氯 化鯨躐基吡啶鑰、氯化本塞鎗（b enzethonium )、及很多 其他者。例示之雙官能性分子包括得自 Akzo Nobel之 Arquad Series及 Armeen Series中之表面活性劑。在一具 體表現中，雙官能性分子是氯化十二烷基三甲基銨，其可 從 Enthone Inc. ( West Haven, CT )獲得，商品名爲 -12- 200907113 PALLADEX ADDITIVE 卜 在另一具體表現中，作爲塗層之雙官能性分子包含胺 及至少一多烷氧化基團。較佳地，雙官能性分子包含胺、 至少一多烷氧化基團及至少一疏水性長鏈烴基。胺部分在 酸性溶液中會變爲陽離子性（一級、二級、三級胺）或爲 永久陽離子性（四級胺）。較佳地，胺是四級胺。多烷氧 化鏈可以包含約2至約20個烷氧基，較佳約2至約1 2個 烷氧基。烷氧基可以是乙氧基、丙氧基、丁氧基或甚至是 彼之組合。烷氧基增加雙官能性分子之親水性。烴基可以 是約6至約24個碳長度。烴基較佳是至少6個碳長度以 有足夠疏水性以在銅奈米粒子周圍形成微胞塗層。烴鏈較 佳不多於約24個碳長度以確保恰當之溶解性。較佳地， 烴鏈比6個碳原子更長且比24個碳原子更短，例如在約8 個碳原子至約1 6個碳原子間，更佳是在約1 0個碳原子至 約1 4個碳原子間。 例示之包含胺及多烷氧化基團之雙官能性分子包括具 有平均介於約8及約22個乙氧化基團之多乙氧化牛脂胺 (例如得自 Akzo Nobel 之 Ethomeen T/20、Ethomeen T/25 及Ethomeen T/30)、具有平均介於約2及約16個多乙氧 化基團之多乙氧化椰胺（cocamine ) (例如得自 Akzo Nobel 之 Ethomeen C/12、Ethomeen C/15 及 Ethomeen C/25)、多丙氧化椰胺（例如propomeen C/12)、多丙氧 化牛脂胺（例如propomeen T/12)、多乙氧化牛脂二胺（ 例如ethoduomeen T/13)、乙氧化/丙氧化之牛脂胺（例 -13- 200907113 如Adsee AB557及Adsee AB600)、具有介於約ι〇及約 20個乙氧化基團之氯化椰子四級錢（例如Ethoquad C/15 、Ethoquad C/25)、具有介於約2及約15個乙氧化基團 之氯化牛脂四級錢（例如Ethoquad T/12、Ethoquad T/15 、及 Ethoquad T/25)。 在另一具體表現中’作爲塗層之雙官能性分子是以乙 二胺爲底質之非離子性ΕΟ/Ρ Ο嵌段共聚物。這些非離子性 聚合物是以 Tetronic®之商品名售出且可得自 BASF Corporation Performance Chemicals ( Mount Olive, NJ 07828)。可應用之Tetronic®表面活性劑包括Tetronic® 5 0 4、Tetronic® 704、Tetronic® 904、Tetronic® 90 8、 Tetronic® 901 、 Tetronic® 13 0 1 、 Tetronic® 1 3 07 、200907113 IX. INSTRUCTIONS OF THE INVENTION [Technical Field of the Invention] The present invention relates generally to through-hole charging techniques using copper metallization and, in particular, to via-through charging techniques for through-via vias using copper nanoparticles. [Prior Art] The integrated circuit (1C) device includes via holes that form electrical connections between the layers of the interconnect structure. In one version, the through hole may extend from the rear side of the 1 c mold to the front side (the active side of the mold). This type of via structure is known in the art as a "straight through via" (TSV). In some devices, the through vias may form an interconnection between one of the bonded wafers in the wafer stack. The depth of the TSV is a function of the thickness of the wafer' which may be from about 30 microns to about 5,000 microns, such as about 250 microns. In the state of the art, the via opening in the TSV has an entrance size of, for example, from about 1 micron to about 200 microns, such as between about 1 〇 microns and about 50 microns. Electrolytic copper metallization is commonly used in semiconductor integrated circuit (1C) device fabrication to provide electrical interconnection. Conventional electrolytic copper deposition baths can take up to half an hour and most often take up to 20 hours to fill the through-holes. The latter is a major obstacle to commercial applicability. Therefore, there is a need in the art for a faster method of metallizing copper of a TSV-containing device. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide an electrolytic copper filling method for a TSV 200907113 which is economical and achieves high quality charging. Briefly, therefore, the present invention is directed to an electrolytic copper plating composition for use in metallizing via features in a semiconductor integrated circuit substrate. The composition comprises coated copper nanoparticles particles. The particles comprise copper nanoparticles and a bifunctional molecular coating, wherein at least about 90% of the copper nanoparticles have at least one lateral direction of less than about 500 nanometers. The size 'and at least about 90% of the copper nanoparticles have at least one transverse dimension greater than about 5 nanometers. The invention further relates to a method for electrolytically depositing copper in a substrate of a semiconductor integrated circuit device, the substrate comprising a via feature having a bottom, a sidewall, and a top opening, the top opening having an entrance dimension of at least 1 micron. The method comprises immersing a semiconductor integrated circuit device substrate in an electrolytic plating composition comprising coated copper nanoparticles, wherein the coated copper nanoparticles comprise copper nanoparticles and a bifunctional molecular coating, Wherein at least about 90% of the copper nanoparticles have at least one transverse dimension of less than about 500 nanometers, and at least about 90% of the copper nanoparticles have at least one transverse dimension greater than about 5 nanometers; and current supply The composition is electrolyzed to deposit copper on the substrate and in the via features. Other objects and features are apparent in part and are indicated in part below. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of through-hole metallization in the fabrication of semiconductor integrated circuit devices. The method of the present invention is particularly useful in a defect-free via-hole overfill process in which a through-pass via is commercially available at a ratio that is commercially implementable. The “no defect” through-hole overfilling method is characterized by good seed layer coverage, electrolytic solution-6-200907113. The bottom of the through hole is properly wetted down, and the inhibitor/leveler and accelerator action are acceptable. The balance is achieved by achieving a fast bottom-up charge and a suitable quality transfer. This method achieves a fully metallized via. See Figure 1 A. Defects resulting from imperfect methods include seams (see Figure 1 B) and voids (see Figure 1C). Conformal often occurs seams, which often result in incorrect waveforms due to improper accelerators and/or deposition methods in the electrolytic solution. The occurrence of voids due to hoops' is often due to the non-optimal balance between the inhibitor/leveler and accelerator action and the use of incorrect waveforms. One aspect of the invention relates to copper particles for TSV charging. Electrolytic copper deposition bath. In particular, the electrolytic copper deposition bath comprises copper particles having a lateral dimension of at least one nanometer. These copper particles are referred to herein as copper nanoparticles. The electrolytic copper plating composition of the present invention may comprise a copper nanoparticle source and a copper ion source. Preferably, the amount of 'copper nanoparticle and copper ion source is the ratio of the coated copper nanoparticle concentration (in grams per liter of copper nanoparticles/liter) to the copper ion concentration (in grams per liter). Between about 0. 00 5 and about 0.4, preferably between about 0.01 and about 〇. In other words, the concentration of copper ions (in grams per liter) is typically 5 to 100 times the concentration of coated copper nanoparticles (in grams per liter). Copper nanoparticle refers to copper particles of at least about 90°/. The particles have at least one transverse dimension ' less than 500 nanometers ("nm") and at least about 90% of the particles have at least one transverse dimension greater than 5 nanometers. Preferably at least about 90% of the particles have at least one less than 5 0 The lateral dimension of the nanometer 'and at least about 90% of the particles have at least one transverse dimension greater than 20 nanometers. Even more preferably 200907113, more preferably, the particle size distribution of the copper particles used in the method of the invention is such that at least about 90% of the particles have at least one transverse dimension of less than 250 nanometers and at least about 90% of the particles have at least A lateral dimension greater than 100 nanometers. In a preferred embodiment, at least 90% of the particles are characterized by less than 500 nanometers of all lateral dimensions of the particles. All percentages herein are by weight unless otherwise stated. Copper nanoparticles in a variety of shapes are available, such as spheres, oblate ellipsoids, oblong ellipsoids, platelets, flakes, cones, barrels, and rods. Regarding the spherical copper nanoparticle, the nanoparticle is usually an irregularly shaped sphere (i.e., a turf, a protrusion, etc., which has a shape which deviates from a perfect sphere). With respect to the irregular spherical copper nanoparticle, the lateral dimension of the at least one nanometer is substantially the diameter of the nanoparticle. Copper nanoparticles having a substantially oblate ellipsoid shape may be defined by three vertical transverse dimensions, two semi-major axes and one semi-secondary axis, and at least about 90% of the flat particles have at least one less than 500 nanometers. Transverse dimension, and at least about 90% of the flat particles have at least one transverse dimension greater than 5 nanometers. Preferably, at least about 90% of the flat particles have at least one transverse dimension of less than 500 nanometers, and at least about 90% The flat particles have at least one transverse dimension greater than 20 nanometers. Preferably, all three transverse dimensions of at least 90% of the flat particles are between about 20 nm and about 5,000 nm, and even more preferably all three transverse dimensions are between about 100 nm and about 250 nm. . The copper nanoparticles having a shape of a flat oblong ellipsoid are also defined by three vertical transverse dimensions, one semi-major axis and two semi-secondary axes, and at least about 90% of the oblong particles have at least one less than 500. The lateral dimension of the nanometer and at least 200907113 about 90% of the oblate particles have at least one transverse dimension greater than 5 nanometers, preferably at least about 90% of the oblong particles have at least one transverse dimension of less than 500 nanometers. Dimensions, and at least about 90% of the elongate particles have at least one transverse dimension greater than 20 nanometers. Preferably, all three transverse dimensions of at least 90% oblate spheroids are between about 20 nm and about 5,000 nm. Even more preferably all three lateral dimensions are about 1 〇〇 nanometer and about 25 0 nm room. Small plates, barrels, rods, cones and sheets can also be defined in view of the lateral dimensions. With respect to each of these shapes, at least about 90% of the particles have at least one transverse dimension of less than 500 nanometers, and at least about 90% of the particles have at least one transverse dimension greater than 5 nanometers; preferably, at least about 90 The % particles have at least one transverse dimension ' less than 500 nanometers' and at least about 90% of the particles have at least one transverse dimension greater than 20 nanometers; even more preferably, at least about 90% of the particles have at least one less than 2 The lateral dimension of 50 nanometers, and at least about 90% of the particles have at least one transverse dimension greater than 100 nanometers. Preferably, each of the nanoparticle shapes has a transverse dimension of less than 500 nanometers and greater than 20 nanometers. In a preferred embodiment, the copper nanoparticles are irregularly shaped spheres wherein at least 90% of the particles have a diameter of less than 500 nanometers and at least about 90% of the particles have a diameter greater than 20 nanometers; preferably. Ground, at least about 90% of the particles have a diameter of less than 250 nanometers, and at least 90% of the particles have a diameter greater than 100 nanometers. Copper nanoparticles are available in the particle size distribution range, and the particle size distribution for a particular application is selected according to the size of the via to be metallized. In order to fill a through hole having a larger opening diameter to ensure a commercially available charge ratio of -9 to 200907113, larger particles are preferred; however, 'to fill a through hole having a smaller opening diameter to It is preferred to ensure that there are no voids to fill the smaller particles. The copper nanoparticles that can be selected to have a smaller opening diameter (e.g., less than about 1 〇 micron) can be selected wherein at least about 8 〇 ° / ° particles have at least one between about 20 and about 50 nm. The size of the person. A copper nanoparticle that can be selected to fill a via having a larger opening diameter (e.g., greater than about 10 microns) is one in which at least 90% of the particles have at least one dimension between about 50 nanometers and about 300 nanometers. By. It has been found that nanoparticles accelerate the deposition rate by acting as seed particles (which can form copper plating around them) and as seed particles in the deposition metallization. In the second aspect, the copper nanoparticles increase the charge rate compared to the conventional metallization using an electrolytic plating bath in which the deposited metal source is composed of copper atoms. Further, the copper deposition method of the present invention substantially produces a void-free and defect-free metallized via. Copper nanoparticles useful in the process of the invention are available from a number of sources. Sources that can be applied include ND C0PPer p〇wder C1_250 (copper spheres with an average diameter of about 250 nm) and ND Copper Powder Cl-500 (copper spheres with an average diameter of about 500 nm) (both from NanoDynamics) (Buffalo, NY)), and Copper Powder 20-9008 (which is also available from NanoDynamics). Copper nanoparticles can be prepared prior to addition to the electrolytic copper deposition bath. The nanoparticle preparation may comprise cleaning particles to remove surface oxides; and treating the particles in a surfactant solution to disperse the particles in the aqueous solution. The cleaning solution suitable for removing the surface oxide is preferably strongly acidic and may contain an organic acid and an inorganic acid. Preferably, the cleaning solution has a pH of between about 1.4 and -10-200907113 of about 3.4, such as between about 1.8 and about 3, such as about 2.4. Inorganic acids which may be used include mineral acids such as hydrofluoric acid, phosphoric acid and hydrochloric acid. The use of strong oxidizing mineral acids such as nitric acid should be avoided. Useful organic acids included in the cleaning solution include acetic acid, trichloroacetic acid, and trifluoroacetic acid. In one embodiment, the copper nanoparticles are cleaned with a solution comprising concentrated acetic acid and hydrofluoric acid (5%) to remove surface oxides. The particles can be cleaned by impregnating the particles with a cleaning solution or by spraying. Cleaning is typically carried out for about 1 minute to about 5 minutes to ensure proper removal of surface oxides. Cleaning for more than 5 minutes does not provide further cleaning. The temperature of the cleaning solution may range from about 18 ° C to about 25 ° C. The particles are not washed after cleaning to avoid re-oxidation of the surface. After cleaning, the copper nanoparticles are coated with bifunctional molecules. The bifunctional molecule comprises a hydrophobic group and a hydrophilic group. The hydrophobic group interacts with the copper nanoparticle during the coating of the nanoparticle in the solution containing the bifunctional molecule; but the hydrophilic group and the aqueous solution (typically a copper-sulfuric acid electrolytic solution containing, for example, an organic additive) There is interaction. By interacting with copper ions in this manner, the bifunctional molecules allow the copper nanoparticles to be dispersed in an aqueous solution, such as a microcapsule coating of bifunctional molecules around the copper nanoparticles. In addition, since the nanoparticles are similarly charged (e.g., being positively charged in a preferred embodiment), the bifunctional coating inhibits agglomeration of the copper nanoparticles. Therefore, the particle size distribution of the copper nanoparticles in the solution remains substantially the same as the particle size distribution of the dried copper nanoparticles, except that the particle size is slightly increased due to the bifunctional coating. Bifunctional molecules can be neutral or positively charged. Preferably, the number of 'bifunctional molecules has a total positive charge such that the coated copper nanoparticles -11 - 200907113 are loaded with a total positive charge. A positive charge is desirable because the wafer substrate containing the through vias serves as a cathode (negatively charged electrode) during electrolytic copper deposition. Thus, when the rectifier (i.e., the power supply) is turned on, the coated copper nanoparticles are electrostatically or electrodynamically drained to the wafer surface. In a specific embodiment, the bifunctional molecule as a coating material comprises an amine and at least one hydrophobic long chain hydrocarbon group. The amine moiety represents a hydrophilic head group and may become cationic (primary, secondary, tertiary amine) or permanent cationic (quaternary amine) in an acidic solution. Preferably, the amine is a quaternary amine. The long chain hydrocarbyl group represents a hydrophobic tail group. The hydrocarbyl group can be from about 6 to about 24 carbons in length. The hydrocarbyl group is preferably at least 6 carbons in length to be sufficiently hydrophobic to form a microcell coating around the copper nanoparticles. The hydrocarbon chain is preferably no more than about 24 carbons in length to ensure proper solubility. Preferably, the hydrocarbon chain is longer than 6 carbon atoms and shorter than 24 carbon atoms, such as between about 8 carbon atoms and about 16 carbon atoms, more preferably about 1 carbon atom and about 1 carbon atom. Between 4 carbon atoms. Exemplary bifunctional molecules comprising an amine and a hydrocarbyl group include dodecyltrimethylammonium chloride (for example, Arquad 12-35W from AkzoNobel), dodecyldimethylbenzylammonium chloride; Hexyltrimethylammonium (eg Arquadl 6-29 and Arquadl 6-29); octadecyltrimethylammonium chloride; octadecyldimethylbenzylammonium chloride; tallow benzyl dimethyl chloride Ammonium, chlorinated whaleyl pyridinium, chlorinated ben guns (b enzethonium ), and many others. Exemplary bifunctional molecules include surfactants from the Arquad Series and Armeen Series of Akzo Nobel. In one embodiment, the bifunctional molecule is dodecyltrimethylammonium chloride available from Enthone Inc. (West Haven, CT) under the tradename -12-200907113 PALLADEX ADDITIVE in another specific In the performance, the bifunctional molecule as a coating comprises an amine and at least one polyalkyl oxide group. Preferably, the bifunctional molecule comprises an amine, at least one polyalkyl oxide group and at least one hydrophobic long chain hydrocarbon group. The amine moiety will become cationic (primary, secondary, tertiary amine) or permanent cationic (quaternary amine) in an acidic solution. Preferably, the amine is a quaternary amine. The polyalkoxy chain may comprise from about 2 to about 20 alkoxy groups, preferably from about 2 to about 12 alkoxy groups. The alkoxy group can be an ethoxy group, a propoxy group, a butoxy group or even a combination thereof. The alkoxy group increases the hydrophilicity of the bifunctional molecule. The hydrocarbyl group can be from about 6 to about 24 carbons in length. The hydrocarbyl group is preferably at least 6 carbons in length to be sufficiently hydrophobic to form a microcellular coating around the copper nanoparticles. The hydrocarbon chain is preferably no more than about 24 carbons in length to ensure proper solubility. Preferably, the hydrocarbon chain is longer than 6 carbon atoms and shorter than 24 carbon atoms, such as between about 8 carbon atoms to about 16 carbon atoms, more preferably about 10 carbon atoms to about 1 between 4 carbon atoms. Exemplary bifunctional molecules comprising amine and polyalkoxy groups include polyethoxylated tallow amines having an average of between about 8 and about 22 ethoxylated groups (e.g., Ethomeen T/20, Ethomeen T from Akzo Nobel). /25 and Ethomeen T/30), a cocamine having an average of between about 2 and about 16 polyethoxylated groups (e.g., Ethomeen C/12, Ethomeen C/15 from Akzo Nobel and Ethomeen C/25), polypropoxylanamide (eg propomeen C/12), polypropoxylated tallow amine (eg propomeen T/12), polyethoxylated tallow diamine (eg ethoduomeen T/13), ethoxylated / propyl Oxidized tallow amine (Example-13-200907113 such as Adsee AB557 and Adsee AB600), chlorinated coconut four-grade money with an amount of about ι〇 and about 20 ethoxylated groups (eg Ethoquad C/15, Ethoquad C/25) a chlorinated tallow quaternary having between about 2 and about 15 ethoxylated groups (e.g., Ethoquad T/12, Ethoquad T/15, and Ethoquad T/25). In another embodiment, the bifunctional molecule as a coating is a nonionic ruthenium/iridium block copolymer based on ethylenediamine. These nonionic polymers are sold under the trade name Tetronic® and are available from BASF Corporation Performance Chemicals (Mount Olive, NJ 07828). Available Tetronic® surfactants include Tetronic® 5 0 4, Tetronic® 704, Tetronic® 904, Tetronic® 90 8 , Tetronic® 901, Tetronic® 13 0 1 , Tetronic® 1 3 07,
Tetronic® 304、Tetronic® 701 、及 Tetronic® 1107Tetronic® 304, Tetronic® 701, and Tetronic® 1107
Tetronic® 904具有以下所示之結構（1 ): H—(OC2H4 ) 17—(OC3H6) 19 (c3h6〇) ig—(c2h4〇) 17-h \ h2 h2 /Tetronic® 904 has the structure shown below (1): H—(OC2H4) 17—(OC3H6) 19 (c3h6〇) ig—(c2h4〇) 17-h \ h2 h2 /
N-C —C —N H ~~(OC2H4) 17 — ( OCjHg )N-C —C —N H ~~(OC2H4) 17 — ( OCjHg )
(C3H6°)l9-(C2H4°)l7-H (1) 銅奈米粒子在塗覆用漿液中經雙官能性分子塗覆。漿 液典型包含銅奈米粒子、雙官能性分子、水及電解銅澱積 組成物之成分。典型地，在塗覆用漿液中銅奈米粒子之濃 度是在約1克/升及約1 〇克/升間，例如約1 · 〇克/升 及約2.5克/升間。在一具體表現中，銅奈米粒子之濃度 是約1.4克/升。典型地，在塗覆用漿液中雙官能性分子 之濃度是在約0.05克/升及約0.15 .克/升間。在一具體 -14- 200907113 表現中，雙官能性分子之濃度是約0.1克/升。濃度部分 地被選擇以確保銅奈米粒子被適當地塗覆，且因此可以用 雙官能性分子濃度對銅奈米粒子濃度之比例來表示。奈米 粒子在攪動（例如攪拌、搖盪等）下被塗覆，且當觀察到 奈米粒子在沒有攪動時仍不沉澱或附聚且組成物之顏色是 安定的情況下，銅奈米粒子被恰當地塗覆。未經塗覆之奈 米粒子若未合適地被塗覆時則特別易於氧化，此可藉溶液 顏色改變而觀察到。 使用經塗覆之銅奈米粒子於電解銅澱積浴中以供半導 體積體電路基板製造中通孔及直通矽通孔之金屬化。電解 銅澱積浴可以另外包含銅離子源、酸、及超塡充添加劑。 這些超塡充添加劑典型包括抑制劑、均平劑、及加速劑。 上列之添加劑應用於高銅金屬/低酸電解電鍍浴、低銅金 屬/高酸電解電鍍浴、及中酸/高銅金屬電解電鍍浴中。 組成物也可包含在此技藝中已知的其他添加劑，例如鹵化 物、粒子精煉劑、四級胺、聚硫醚化合物、及其他。 在電解銅源積浴中銅奈米粒子濃度可以在約1克/升 及約1 〇克/升間，例如在約1 _ 5克/升及約2 · 5克/升間 〇 本發明之銅電鍍組成物所用之抑制劑包括一群包含共 價鍵結至一級胺、二級胺、三級胺及四級胺之多醚基團的 抑制劑及一群包含共價鍵結至一級醇、二級醇、及多元醇 之多醚基團的抑制劑。多醚類包含氧化乙烯重複單元、氧 化丙烯重複單元及其組合之鏈。例如共價鍵結至胺類的多 -15- 200907113 醚抑制劑描述於美國專利7,3 03，992，其在2007年12月4 日公告，其整個揭示明確地倂入作爲參考。 本發明之抑制劑化合物具有在約1 0 0 0至約3 0,0 0 0間 之分子量。藉由以下結構（2 )至（6 )顯示例示之抑制劑 化合物，其包含共價鍵結至陽離子性物質之多醚基團，其 中多酸共價鍵結至氮原子。要注意：在一具體表現中，本 發明之電解銅電鍍組成物可以包含經塗覆的銅奈米粒子（ 其經塗覆以乙二胺爲底質之非離子性EO/PO嵌段共聚物） ，同時另外包含此種共聚物作爲抑制劑。在此具體表現中 ，以乙二胺爲底質之非離子性EO/PO嵌段共聚物係作爲抑 制劑及雙官能性表面活性劑以使銅奈米粒子分散於溶液中 結構（2 )是具有以下結構之乙二胺的PO/EO嵌段共 聚物： H (〇C2H4)n (〇C3H6)m /(C3H6〇）m- —(C2H40)n· —H \ h2 h2 / N— / —C -C -N H-(OC2H4)n (〇C3H6)/ (C3H6〇)m- —(C2H40)n· 一 H (2) 且其中η可以是在1至約3 0間且m可以是在1至約 3 0間。因此，具有結構（5 )之抑制劑化合物包含共約4 至約120個PO重複單元及共約4至約120個EO重複單 元於四個PO/EO嵌段共聚物上。於單—PO/EO嵌段共聚 物上之PO (疏水性單元）嵌段的分子量可以是在約50克 /莫耳至約1800克/莫耳間，且在單一 P0/E0嵌段共聚 物上之EO (親水性單元）嵌段的分子量可以在約4〇克/ -16- 200907113 莫耳至約1400克/莫耳間。單一 p 〇/EO共聚物之分子量 可以在約1〇〇克/莫耳至約3600克/莫耳間。例示之具 有結構（2)之抑制劑化合物是得自BASF Corporation of Mt_ Olive, New Jersey 而商品名爲 Tetronic®704。對於在 全部四個PO/EO嵌段共聚物上之共約52個P〇重複單元 而言，此抑制劑化合物之每一 ΡΟ/EO嵌段共聚物包含約 13個PO重複單元；且對於在全部四個PO/EO嵌段共聚物 上之共約44個E0重複單元而言，此抑制劑化合物之每一 Ρ0/Ε0嵌段共聚物包含約1 1個E0重複單元。因此， Tetronic®704之總Mw是在約5000克/莫耳及約5500克 /莫耳間。其他例示之結構（2 )的嵌段共聚物也可從 BASF Corporation 獲得，商品名爲 Tetronic®504。對於 在全部四個PO/EO嵌段共聚物上之共約36個p〇重複單 元而言，此抑制劑化合物之每一 P 〇/EO嵌段共聚物包含約 9個PO重複單元；且對於在全部四個PO/E〇嵌段共聚物 上之共約3 0個E 0重複單元而言，此抑制劑化合物之每一 Ρ0/Ε0嵌段共聚物包含約7·5個E0重複單元。因此， Tetronic®504之總Mw是在約3200克/莫耳及約3600克 /莫耳間。浴組成物可以包含結構（2 )之嵌段共聚物混 合物。 結構（3 )是具有以下一般結構之乙二胺之N -甲基化 PO/EO嵌段共聚物： -17- 200907113 CH3(C3H6°) l9-(C2H4°)l7-H (1) The copper nanoparticles are coated with a bifunctional molecule in a coating slurry. The slurry typically comprises copper nanoparticles, bifunctional molecules, water and components of the electrolytic copper deposition composition. Typically, the concentration of copper nanoparticles in the coating slurry is between about 1 gram per liter and about 1 gram per liter, such as between about 1 gram per liter and about 2.5 grams per liter. In one embodiment, the concentration of copper nanoparticles is about 1.4 grams per liter. Typically, the concentration of bifunctional molecules in the coating slurry is between about 0.05 grams per liter and about 0.15 grams per liter. In a specific -14-200907113 performance, the concentration of the bifunctional molecule is about 0.1 g/L. The concentration is selected in part to ensure that the copper nanoparticles are suitably coated, and thus can be expressed as a ratio of the concentration of the bifunctional molecules to the concentration of the copper nanoparticles. The nanoparticles are coated under agitation (for example, stirring, shaking, etc.), and when it is observed that the nanoparticles do not precipitate or agglomerate without agitation and the color of the composition is stable, the copper nanoparticles are Appropriately applied. Uncoated nanoparticles are particularly susceptible to oxidation if not properly coated, as can be observed by changing the color of the solution. The coated copper nanoparticles are used in an electrolytic copper deposition bath for metallization of vias and through vias in the fabrication of semiconducting bulk circuit substrates. The electrolytic copper deposition bath may additionally comprise a source of copper ions, an acid, and an overcharge additive. These supercharged additives typically include inhibitors, leveling agents, and accelerators. The additives listed above are used in high copper metal/low acid electrolytic plating baths, low copper metal/high acid electrolytic plating baths, and medium acid/high copper metal electrolytic plating baths. The composition may also contain other additives known in the art, such as halogens, particulate refining agents, quaternary amines, polythioether compounds, and others. The concentration of copper nanoparticles in the electrolytic copper source bath may be between about 1 gram per liter and about 1 gram per liter, for example between about 1 _ 5 gram per liter and about 2 · 5 gram per liter. Inhibitors for copper electroplating compositions include a population of inhibitors comprising a polyether group covalently bonded to a primary amine, a secondary amine, a tertiary amine, and a quaternary amine, and a population comprising a covalent bond to a primary alcohol, An alcohol, and an inhibitor of a polyether group of a polyol. The polyethers comprise chains of ethylene oxide repeating units, oxypropylene repeating units, and combinations thereof. For example, the co-bonding to amines -15-200907113 ether inhibitors are described in U.S. Patent No. 7,3,03,992, issued on Dec. 4, 2007, the entire disclosure of which is expressly incorporated by reference. The inhibitor compound of the present invention has a molecular weight of from about 1,000 to about 3,000. The exemplified inhibitor compound is shown by the following structures (2) to (6), which contains a polyether group covalently bonded to a cationic substance in which a polyacid is covalently bonded to a nitrogen atom. It is to be noted that, in a specific embodiment, the electrolytic copper plating composition of the present invention may comprise coated copper nanoparticles (the nonionic EO/PO block copolymer coated with ethylenediamine as a substrate). ), while additionally containing such a copolymer as an inhibitor. In this specific embodiment, a nonionic EO/PO block copolymer based on ethylenediamine is used as an inhibitor and a bifunctional surfactant to disperse copper nanoparticles in a solution. (2) PO/EO block copolymer of ethylenediamine having the following structure: H (〇C2H4)n (〇C3H6)m /(C3H6〇)m-—(C2H40)n·—H \ h2 h2 / N— / C -C -N H-(OC2H4)n (〇C3H6) / (C3H6〇)m- - (C2H40)n·一H (2) and wherein η can be between 1 and about 30 and m can be 1 to about 30 rooms. Thus, the inhibitor compound having structure (5) comprises from about 4 to about 120 PO repeating units and from about 4 to about 120 EO repeating units on four PO/EO block copolymers. The molecular weight of the PO (hydrophobic unit) block on the mono-PO/EO block copolymer may range from about 50 g/mol to about 1800 g/mol, and in a single P0/E0 block copolymer. The molecular weight of the EO (hydrophilic unit) block may range from about 4 gram / -16 to 200907113 moles to about 1400 grams / mole. The molecular weight of a single p 〇 / EO copolymer can range from about 1 gram per mole to about 3600 grams per mole. An exemplary inhibitor compound having structure (2) is available from BASF Corporation of Mt_ Olive, New Jersey under the trade name Tetronic® 704. For a total of about 52 P〇 repeating units on all four PO/EO block copolymers, each ΡΟ/EO block copolymer of this inhibitor compound contains about 13 PO repeating units; For a total of about 44 E0 repeating units on all four PO/EO block copolymers, each Ρ0/Ε0 block copolymer of this inhibitor compound contains about 11 E0 repeating units. Thus, the total Mw of Tetronic® 704 is between about 5000 grams per mole and about 5500 grams per mole. Other exemplary block copolymers of structure (2) are also available from BASF Corporation under the trade name Tetronic® 504. For a total of about 36 p〇 repeating units on all four PO/EO block copolymers, each P 〇/EO block copolymer of the inhibitor compound comprises about 9 PO repeat units; For a total of about 30 E 0 repeating units on all four PO/E〇 block copolymers, each Ρ0/Ε0 block copolymer of this inhibitor compound contains about 7.5 E0 repeating units. Thus, the total Mw of Tetronic® 504 is between about 3200 grams per mole and about 3600 grams per mole. The bath composition may comprise a block copolymer mixture of structure (2). Structure (3) is an N-methylated PO/EO block copolymer of ethylenediamine having the following general structure: -17- 200907113 CH3
Η—(〇C2H4)n-(〇C3H6)m H2 H2 I /(C3H60)m-(C2H40)n-HΗ—(〇C2H4)n-(〇C3H6)m H2 H2 I /(C3H60)m-(C2H40)n-H
H—(OC2H4)n-(〇C3H6)m/ + ^(C3H6〇)m-(C2H4〇)n-H (3), 其中n可以在1至約3 0間且m可以是在1至約3 〇間 。具有結構（3 )之抑制劑化合物來源是N -甲基化0 Tetronic® 504 或 N-甲基化之 Tetronic® 704。 結構（4 )是具有以下一般結構之乙二胺的甲基封@ 之PO/EO嵌段共聚物： CH3—(〇C2H4)n—(OC3H6)m、 H2 H2 /(C3H60)m—(〇2Η4〇)η 一 CH3 N-C——C——N、 CH3-(OC2H4)n—(OC3H5)/ (C3H60) m— (C2H4〇) n-CH3 (4)/ 且其中n可以在1至約3 0間且m可以是在1至約3 0 間。具有結構（4 )之抑制劑化合物來源是甲基封端= Tetronic® 504或甲基封端之Tetronic® 704。在不同之替 代方式中，末端氧原子之一者可以鍵結至甲基且另外三個1 末端氧原子可以鍵結至氫原子；或末端氧原子之二者可» 鍵結至甲基且末端氧原子之二者可以鍵結至氣原子，或末 端氧原子之三者鍵結至甲基且末端氧原子之一者可以鍵結 至氫原子；或所有末端氧原子可以鍵結至甲基。 在另一替代方式中，嵌段共聚物如上述地被甲基化且 封端’只要濁點是使彼能與銅溶液相容者。 結構（5 )是具有以下一般結構之乙二胺的 Ρ0/Ε0/Ρ0三嵌段共聚物： H~(OC3H6)。一~i〇C2H4)n-(OC3H6)m η, H2 ^(C3H60) m^(C2H40) n-(C3H6〇) 〇Ή *N-C —C —H—(OC2H4)n-(〇C3H6)m/ + ^(C3H6〇)m-(C2H4〇)nH (3), wherein n may be from 1 to about 30 and m may be from 1 to about 3 〇 between. The source of the inhibitor compound having structure (3) is N-methylated 0 Tetronic® 504 or N-methylated Tetronic® 704. The structure (4) is a PO/EO block copolymer of a methyl group of ethylene having the following general structure: CH3—(〇C2H4)n—(OC3H6)m, H2H2/(C3H60)m—(〇) 2Η4〇)η一CH3 NC——C——N, CH3-(OC2H4)n—(OC3H5)/(C3H60) m—(C2H4〇) n-CH3 (4)/ and where n can be from 1 to about 3 0 and m can be between 1 and about 30. The source of the inhibitor compound having structure (4) is methyl terminated = Tetronic® 504 or methyl terminated Tetronic® 704. In a different alternative, one of the terminal oxygen atoms may be bonded to the methyl group and the other three terminal oxygen atoms may be bonded to the hydrogen atom; or both of the terminal oxygen atoms may be bonded to the methyl group and terminated Both of the oxygen atoms may be bonded to the gas atom, or the three terminal oxygen atoms may be bonded to the methyl group and one of the terminal oxygen atoms may be bonded to the hydrogen atom; or all of the terminal oxygen atoms may be bonded to the methyl group. In another alternative, the block copolymer is methylated and capped as described above as long as the cloud point is such that it is compatible with the copper solution. The structure (5) is a Ρ0/Ε0/Ρ0 triblock copolymer having the following general structure of ethylenediamine: H~(OC3H6). I~i〇C2H4)n-(OC3H6)m η, H2 ^(C3H60) m^(C2H40) n-(C3H6〇) 〇Ή *N-C —C —
H-(OC3H6) 〇~(0C2h4 ) n一 (A%) / (C3H6〇)m-(C2H4〇)n-(C3H6〇)〇-H (5), -18- 200907113 且其中η可以在1至約3 0間，m可以是在1至約3 0 間且〇可以在約1至約5間，或使濁點能與銅溶液相容者 。較佳地，〇是1或2。具有結構（5 )之抑制劑化合物來 源是Ρ0封端之Tetronic® 504或Ρ〇封端之Tetronic® 704 °H-(OC3H6) 〇~(0C2h4) n-(A%) / (C3H6〇)m-(C2H4〇)n-(C3H6〇)〇-H (5), -18- 200907113 and wherein η can be 1 To about 30, m can be between 1 and about 30 and the enthalpy can be between about 1 and about 5, or the cloud point can be compatible with the copper solution. Preferably, 〇 is 1 or 2. The inhibitor compound with structure (5) is Ρ0 terminated Tetronic® 504 or Ρ〇 terminated Tetronic® 704 °
結構（6)是具有以下結構之三乙二醇二胺的PO/EO 嵌段共聚物：Structure (6) is a PO/EO block copolymer of triethylene glycol diamine having the following structure:
H—(OC2H4)n-(OC3H6)m\ /(C3H60)m-(C2H40)n-H /\ /\ /〇\ /\ H—(〇C2H4)n—(OC3H6>m’ H2CH2C CH2CH2 CH2CH2 (。3%〇) m—(C2H4〇) n_H (6), 且其中n可以在1至約3 0間且m可以是在1至約3 0 間。可從 Huntsman LLC of Salt Lake City，Utah 獲得商品 名爲Jeffamine XTJ-504之三乙醇二胺，而PO/EO可共價 鍵結至此三乙醇二胺。在具有結構（6 )之抑制劑化合物 中PO/EO共聚物結構可以與Tetronic® 5 04及Tetronic® 704中之PO/EO共聚物實質相同。因此，具有結構（6 ) 之抑制劑化合物的M w可以在約5 2 0 0克/莫耳及約5 8 0 0 克/莫耳間。 本發明組成物也可包括均平劑。例示之均平劑揭示於 2008年1月8日公告之美國專利7,316,772中，其整個揭 示明確地倂入作爲參考。一種較佳之均平劑是苄基氯及羥 乙基聚乙一亞胺之反應產物，其可得自Enthone Inc. of West Haven，Connecticut，商品名爲 ViaForm® Leveler。 另一適合之均平劑是苄基氯及聚乙二亞胺之反應產物。另 -19- 200907113 外適合之均平劑是i-氯甲基萘及羥乙基聚乙二亞胺之反應 產物（可從 BASF Corporation of Rensselear, New York 獲 得，商品名爲Lupasol SC 61B)。聚乙烯基吡啶及其四級 鹽，及聚乙烯基咪唑及其鹽也是適合的。這些均平劑可以 混合成濃度，例如，約〇 · 1毫升/升及約2 5毫升/升間 ，例如約4毫升/升。任意地，其他型式之另外的均平化 合物可倂入浴中。 另外之均平劑揭示於2004年10月12日申請之美國 專利公開案20〇5/0〇45 48 8中，其整個揭示明確地併入作 爲參考。其中所揭示之均平劑包括一般爲烷基化之4 -乙烯 基吡啶及2-乙烯基吡啶之衍生物。在一些具體表現中，這 些均平劑也是吡啶基聚合物。其中所揭示之例示的均平劑 包括4-乙烯基吡啶與硫酸甲酯之反應產物、聚（4-乙烯基 吡啶）與硫酸甲酯之反應產物、聚（4 -乙烯基吡啶）與硫 酸二甲酯之反應產物、聚（4 -乙烯基吡啶）與甲苯磺酸甲 酯之反應產物、4 -乙烯基吡啶與硫酸二甲酯之反應產物、 4-乙烯基吡啶與甲苯磺酸甲酯之反應產物、4-乙烯基吡啶 與2-氯乙醇之反應產物、4-乙烯基吡啶與苄基氯之反應產 物、4-乙烯基吡啶與烯丙基氯之反應產物、4-乙烯基吡啶 與4-氯甲基吡啶之反應產物、4-乙烯基吡啶與1，3-丙烷萘 迫磺內酯之反應產物、4-乙烯基吡啶與甲苯磺酸甲酯之反 應產物、4-乙烯基吡啶與氯丙酮之反應產物、4-乙烯基吡 啶與2-甲氧基乙氧基甲基氯之反應產物、4-乙烯基吡啶與 2 -氯乙基醚之反應產物' 2 -乙烯基吡啶與甲苯酸甲酯之反 -20 - 200907113 應產物、2 -乙烯基卩比π定與硫酸二甲醋之反應產物、聚（2 _ 甲基-5 -乙烯基吡啶）、及1 -甲基—4 -乙烯基吡啶_三氟甲 磺酸鹽。均平劑混合成濃度，例如，約〇.丨毫克/升至約 25毫克/升。 組成物也包含加速劑。例示之加速劑是如美國專利 6,776,8 93中所揭示之浴可溶的有機二價硫化合物，該專 利之整個揭示明確地倂入作爲參考。在一較佳具體表現中 ，加速劑相對應於式（7 )H—(OC2H4)n-(OC3H6)m\ /(C3H60)m-(C2H40)nH /\ /\ /〇\ /\ H—(〇C2H4)n—(OC3H6>m' H2CH2C CH2CH2 CH2CH2 (.3 %〇) m—(C2H4〇) n_H (6), and where n can be between 1 and about 30 and m can be between 1 and about 30. Trade names are available from Huntsman LLC of Salt Lake City, Utah. It is Jeffamine XTJ-504 triethanol diamine, and PO/EO can be covalently bonded to this triethanol diamine. The PO/EO copolymer structure in the inhibitor compound with structure (6) can be combined with Tetronic® 5 04 and The PO/EO copolymer in Tetronic® 704 is substantially the same. Thus, the Mw of the inhibitor compound having structure (6) can be between about 520 g/mole and about 580 g/mole. The composition of the present invention may also include a leveling agent. The exemplified leveling agent is disclosed in U.S. Patent No. 7,316,772, issued Jan. 8, 2008, the entire disclosure of which is expressly incorporated by reference. The reaction product of chlorine and hydroxyethyl polyethyleneimine, available from Enthone Inc. of West Haven, Connecticut, under the trade name ViaForm® Leveler. Another suitable leveling agent is benzyl chloride and poly The reaction product of diimine. Another -19-200907113 The suitable leveling agent is the reaction product of i-chloromethylnaphthalene and hydroxyethylpolydiimide (available from BASF Corporation of Rensselear, New York) It is also known as Lupasol SC 61B). Polyvinylpyridine and its quaternary salt, and polyvinylimidazole and its salts are also suitable. These leveling agents can be mixed into a concentration, for example, about 1 ml/L and about 2 Between 5 ml/L, for example about 4 ml/L. Optionally, other homogenous compounds of other types can be incorporated into the bath. Further homogenizers are disclosed in U.S. Patent Publication No. 20, filed on Oct. 12, 2004. The entire disclosure is expressly incorporated by reference in its entirety. In particular, these leveling agents are also pyridyl polymers. The exemplified leveling agents disclosed include the reaction product of 4-vinylpyridine with methyl sulfate, poly(4-vinylpyridine) and methyl sulfate. Reaction product, poly(4-vinylpyridine) and Reaction product of dimethyl sulfate, reaction product of poly(4-vinylpyridine) and methyl tosylate, reaction product of 4-vinylpyridine and dimethyl sulfate, 4-vinylpyridine and toluenesulfonic acid The reaction product of the ester, the reaction product of 4-vinylpyridine and 2-chloroethanol, the reaction product of 4-vinylpyridine and benzyl chloride, the reaction product of 4-vinylpyridine with allyl chloride, 4-vinyl Reaction product of pyridine with 4-chloromethylpyridine, reaction product of 4-vinylpyridine with 1,3-propane naphthalene lactone, reaction product of 4-vinylpyridine with methyl tosylate, 4-ethylene Reaction product of pyridine with chloroacetone, reaction product of 4-vinylpyridine with 2-methoxyethoxymethyl chloride, reaction product of 4-vinylpyridine with 2-chloroethyl ether '2-vinyl Reverse -20 of pyridine and methyl toluate - 200907113 The reaction product of product, 2 -vinyl ruthenium ratio π and dimethyl sulphate, poly(2 _ methyl-5 -vinyl pyridine), and 1-A 4--4-vinylpyridine-trifluoromethanesulfonate. The leveling agent is mixed to a concentration of, for example, about 丨.丨mg/liter to about 25 mg/liter. The composition also contains an accelerator. The exemplified accelerators are bath-soluble organic divalent sulfur compounds as disclosed in U.S. Patent No. 6,776,8, the entire disclosure of which is expressly incorporated by reference. In a preferred embodiment, the accelerator corresponds to equation (7)
Ri- ( S ) nRX〇3M ( 7 ) 其中 Μ是氫、鹼金屬或錢，其視需要以滿足價數； X是S或Ρ ; R是1至8個碳原子之伸烷基或伸環烷基，6至12個 碳原子之芳族烴或脂族芳族烴； η是1至6 ;且Ri- ( S ) nRX〇3M ( 7 ) wherein hydrazine is hydrogen, alkali metal or money, as needed to satisfy the valence; X is S or hydrazine; R is an alkyl or exfoliating ring of 1 to 8 carbon atoms An alkyl group, an aromatic hydrocarbon of 6 to 12 carbon atoms or an aliphatic aromatic hydrocarbon; η is 1 to 6;
Ri是M03XR，其中Μ、Χ及R如上定義。 特佳之加速劑是下式（8 )之3 , 3 ’ -二硫基雙（1 -丙烷 磺酸）二鈉鹽（“SPS”）： 〇 f II . + S (CH2) 〇-S 〇 NaRi is M03XR, wherein Μ, Χ and R are as defined above. A particularly preferred accelerator is 3,3'-dithiobis(1-propanesulfonic acid) disodium salt ("SPS") of the following formula (8): 〇 f II . + S (CH2) 〇-S 〇 Na
II 〇 〇 S (CH2) 3 S-0 Na+ -21 - 200907113 加速劑典型之混合濃度是在約〇 · 5毫升/升及約1 ο 〇 ο 毫升/升間，更典型是在約Ο·5毫升/升及約50毫升/ 升間，例如在約2毫升/升及約5 0毫升/升間’例如在 約5毫升/升及30毫升/升間。在一具體表現中’使用 10毫升/升之SPS。 電解銅電鍍浴之成分可以依照欲被電鍍之基板而廣泛 地變化。電解浴包括酸浴及鹼浴。不同之電解銅電鍍浴描 述於標題爲 Modern Electroplating,之書中，F.A. Lowenheim, John Reily & Sons, I n c., 1 9 7 4 編輯，第 183- 203頁。例示之電解銅電鍍浴包括氟硼酸銅、焦磷酸銅、 氰化銅、膦酸銅、乙酸銅、硫酸銅及其他銅金屬錯合物， 例如甲烷磺酸。大部分之典型的電解銅電鍍浴包含硫酸銅 或甲烷磺酸銅於酸溶液中。 因此，銅離子及酸之濃度可以在廣範圍內變化；例如 ，約4至約1 3 5克/升之銅離子，較佳約4 0至約1 0 0克 /升之銅離子，及約2至約2 2 5克/升之酸，較佳約1 0 至約5 0克/升之酸。在一具體表現中，銅源是以硫酸銅 爲底質之來源之一’亦即硫酸銅或硫酸銅五水合物。在另 一具體表現中，銅源是甲烷磺酸銅。在銅源爲以硫酸鹽爲 底質之來源的具體表現中’銅濃度範圍典型是約5克/升 至約75克/升’例如約5克/升至約30克/升，或約30 克/升至約75克/升。甲烷磺酸銅是更可溶之銅來源， 且銅濃度範圍可以更廣’例如約5克/升至約1 3 5克/升 ’例如約75克/升至約135克/升，或約4〇克/升至約 -22- 200907113 100克/升。。在低銅系統中’銅離子濃度可以在約5克 /升至約30克/升間’例如在約8克/升至約25克/升 間。在一些高銅系統中’銅粒子濃度可以在約3 5克/升 至約1 3 5克/升間，例如約3 5克/升至約7 5克/升間， 較佳約35克/升至約60克/升，較佳約75克/升至約 1 3 5克/升間，較佳約1 〇 〇克/升至約丨3 5克/升間。 在電解銅電鍍浴中酸源包括硫酸、甲烷磺酸、磷酸、 乙酸及硼酸。酸濃度範圍可以在約2至約225克/升酸之 間’較佳約1 0克/升至約5 0克/升間。 氯離子也可以用在浴中’其濃度至高達200毫克/升 ’較佳約1 0至9 0毫克/升。添加這些濃度範圍內之氯離 子以加強其他浴添加劑之功能。這些添加劑系統包括加速 劑、抑制劑及均平劑。 在浴中典型可以使用多種添加劑以提供經電鍍銅之金 屬所需之表面精練。經常使用多於一種添加劑，而每一添 加劑形成一所要功能。通常使用至少二種添加劑以開始互 連特徵之由底部往上之塡充，以及改良被鍍金屬的物性（ 例如亮度）、結構性、及電性（例如導電性及可靠性）。 使用特別的添加劑（經常是有機添加劑）以供粒子精煉、 抑制樹枝狀生長、及改良覆蓋本領及電鍍本領。特別想要 之添加劑系統使用芳族或脂族四級胺、聚硫醚化合物及聚 酸之混合物。其他添加劑包括例如硒、碲及硫化合物。 圖2是包含直通矽通孔金屬化之製備晶片-對-晶片疊 層物或小晶片-對-晶片疊層物之方法步驟的流程圖。使用 -23- 200907113 本發明之電解銅澱積溶液之金屬化用之晶片基板（亦即裝 置晶片）包含通孔及直通矽通孔，彼係藉一般已知的光微 影技術及蝕刻方法來製備。在一典型方法中，慣用之光阻 材料藉旋轉塗覆被施加至裝置晶片之已清潔且乾燥之表面 上。光阻材料可以在約6 0 °c至約1 0 0 °c之溫度軟燒烤約5 至3 0分鐘以除去過多之溶劑。在軟燒烤後，以限定銅金 屬化之圖形的方式使光阻材料曝於紫外光。經曝光之光阻 材料而後使用顯影溶液來溶解。限定銅金屬化圖形之晶片 及光阻材料而後被硬燒烤，此典型是在約1 20°C至約1 80 °C間約20至3 0分鐘。經曝光之晶片而後藉此技藝中已知 之方式來鈾刻以限定通孔圖形，該通孔而後被塗覆以阻障 層以抑制銅擴散，該阻障層可爲氮化鈦、鉅、氮化鉅、或 釕。其次，阻障層典型用銅或其他金屬之晶種層來植晶以 在其上開始銅之超塡充電鍍。可以藉化學氣相澱積作用（ CVD ) 、物理氣相澱積作用（PVD )或類似者以施加銅 晶種層。而後使用本發明之電解銅澱積組成物及方法以電 鍍具有阻障層及銅晶種層之通孔。 用於電鍍半導體基板之電鍍裝置是習知的且描述於例 如Haydu等人之美國專利6,〇24,856中。電鍍裝置包含電 解電鍍槽，此槽容納澱積溶液且由適合材料（例如塑膠或 其他對於電解電鍍溶液爲惰性之材料）所製成。該槽可以 是柱狀以特別供晶片電鍍。陰極被水平安置在槽之上部且 可以是任何形式之基板例如具有開口（如溝及通孔）之矽 晶片。陽極也較佳是圓形以供晶片電鍍且被水平安置在槽 -24- 200907113 之下部，以在陽極及陰極間形成一空間。陽極典型是可溶 解之電極，例如銅金屬。 浴添加劑可用於與由不同之工具製造商所發展之膜技 術結合。在此系統中，陽極可以藉膜以與有機浴添加劑隔 離。陰極及有機浴添加劑之分離的目的是要使陽極表面上 有機浴添加劑之氧化作用最小化。 陰極基板及陽極藉接線以分別電連接至整流器（電力 供應器）。用於直流或脈衝電流之陰極基板具有淨負電荷 以致溶液中之銅離子在陰極基板上被還原，以致形成電鍍 之銅金屬於陰極表面上。再者，在陰極上之淨負電荷吸引 淨正電荷之經塗覆的銅奈米粒子，此奈米粒子會黏至晶片 基板。在電鍍操作期間隨著銅離子還原之持續，藉著在奈 米粒子表面之周圍建立之銅金屬化，銅奈米粒子會被環繞 。氧化反應在陽極進行。若使用週期的脈衝逆電鍍，則在 陰極可以進行相同之氧化反應。陰極及陽極可以水平或垂 直安置於槽中。 在電解電鍍系統操作期間，當整流器被施加能量時， 銅金屬被電鍍在陰極基板表面上。可以利用脈衝電流、直 流、週期逆電流、週期脈衝逆電流、或其他適合之電流。 已發現：使用約50至約1 〇〇毫秒之循環的脈衝電流 (亦即施加2 5至5 0毫秒之電流接著是2 5至5 0毫秒之休 息期）產生銅澱積物，與慣用直流電鍍（其從銅金屬化之 來源係由銅離子所組成之浴進行）相比，對於相同電鍍電 流（如總庫侖（C 〇 u 1 〇 m b s )所測量的）而言，此銅殿積物 -25- 200907113 具有較大質量。因此’使用包含銅奈米粒子之浴的脈衝電 鍍在比慣用之電鍍方法更高之電鍍效率情況中’將通孔塡 充。電流密度可以至高約1〇 A/dm2，典型在約0.2 A/dm2 至約6 A/dm2間。較佳使用約1 : 1之陽極對陰極比例，但 此比例也可在約1 : 4至4 : 1間廣泛地變化。在一較佳之具 體表現，使用下述脈衝電流變化曲線以進行電鍍：電流密 度0.3 A/dm2歷時25毫秒，接著休息25毫秒。在另一較 佳具體表現中，使用下述脈衝電流變化曲線以進行電鍍： 電流密度1 A/dm2歷時25毫秒，接著休息25毫秒。 電解溶液之溫度可以使用加熱器/冷卻器來保持，藉 此電解溶液從容納之槽除去且流過加熱器/冷卻器，而後 循環至容納之槽。例如，浴溫度典型是約室溫（例如約 20-27 °C )，但可以在至高約40 °C或更高之高溫。此方法 也在電解電鍍槽中使用混合液，係藉攪動或較佳藉循環流 經槽之再利用的電解溶液流而供應。流經電解電鍍槽之流 提供電解溶液在槽中典型少於約1分鐘之停留時間，更典 型是少於3 0秒之停留時間，例如1 0 - 2 0秒之停留時間。 再次參考圖2。在通孔塡充後，晶片表面及經曝光之 銅金屬化可以藉此技藝中已知的化學機械磨光來清潔。可 以藉慣用之蝕刻技術使晶片變薄以使銅金屬化之底層曝光 ，藉此獲得直通矽通孔，其中銅金屬化從晶片或IC鑄模 的後側延伸至前側，亦即晶片或鑄模之活性側。晶片可以 藉此技藝中已知的方法來進一步加工、堆疊及單切（ singulated )以獲得包含多裝置級層之裝置，每一級層使 -26- 200907113 用直通矽通孔來電連接。 在詳細描述本發明後，明顯的：改良及變化是可能的 且不偏離所附申請專利範圍中所定義之本發明的範圍。 【實施方式】 提供以下非限制性實例以進一步說明本發明。 實例1 :經塗覆之銅奈米粒子 銅奈米粒子塗覆雙官能性分子。銅奈米粒子（2 00奈 米平均直徑）是得自 NanoDymanics Inc. (Buffalo, NY) 之ND銅，且具有一粒子尺寸分布，其中至少約80 %奈米 粒子具有在約1〇〇奈米及約3 00奈米間之直徑。銅奈米粒 子在一包含濃縮乙酸及氫氟酸（5 % )之溶液中清潔以除去 表面氧化物。經清潔之銅奈米粒子在去離子化之蒸餾水中 清洗。 雙官能性分子是氯化十二烷基三甲基銨，其係得自 Enthone Inc. ( West Haven, CT )，商品名爲 pALLADEX ADDITIVE 1。藉添加銅奈米粒子（5.6克/升）及氯化十 二烷基三甲基銨（2毫升/升）至水溶液而製備塗覆用漿 液。溶液另外包含銅離子、硫酸、及氯離子。塗覆用漿液 在室溫下於Corning Stirrer之設定5情況中攪拌約3小時 以在奈米粒子周圍獲得微胞塗層。 實例2:包含銅奈米粒子之電解銅澱積浴 -27- 200907113 製備包含以下成分之電解銅澱積浴（浴A，總體積 2S0毫升）：經塗覆之銅奈米粒子（5.6克/升）；硫酸 銅（50克/升）；硫酸（80克/升）；氯離子（5〇ppm) ;加速劑（1 0毫升/升）；抑制劑（2毫升/升）；均平 劑（4毫升/升）。此浴依照以下方式製備·· 1. 添加250 ¾升電解銅基礎溶液（其包含5〇克/升 銅離子，80克/升硫酸及50ppm氯離子）至400毫升燒 杯中 。 2. 使用微量吸管（WHEATON 20〇-l〇〇〇pL微量吸管 )以添加加速劑（1.2 5毫升）、抑制劑（1 .2 5毫升）及均 平劑（1.25毫升）至此燒杯。 3. 將ND銅奈米粒子（ι_4克）加入燒杯中。 4 .在室溫攪拌此浴3小時。 製備包含以下成分之比較性電解銅澱積浴（比較浴B ，總體積250毫升）：銅離子（50克/升）；硫酸（8〇 克/升）；氯離子（50ppm);加速劑（5毫升/升）； 抑制劑（5毫升/升）；均平劑（5毫升/升）。 實例3 :從實例2之浴的電解銅澱積作用 使用來自實例2之浴A及B以澱積銅層於Hull Cell Panel上。在直流或脈衝電流狀況下以〇.5A電流（2II 〇〇S (CH2) 3 S-0 Na+ -21 - 200907113 The typical mixing concentration of the accelerator is between about 毫升 5 ml / liter and about 1 ο 〇 ο cc / liter, more typically at about Ο · 5 Between liters/liter and about 50 ml/liter, for example between about 2 ml/liter and about 50 ml/liter, for example between about 5 ml/liter and 30 ml/liter. In a specific performance 'use 10 ml / liter of SPS. The composition of the electrolytic copper plating bath can be widely changed depending on the substrate to be plated. The electrolytic bath includes an acid bath and an alkali bath. Different electrolytic copper plating baths are described in the book Modern Electroplating, F.A. Lowenheim, John Reily & Sons, I n c., 1 9 7 4 Edit, pp. 183-203. Exemplary electrolytic copper plating baths include copper fluoroborate, copper pyrophosphate, copper cyanide, copper phosphonate, copper acetate, copper sulfate, and other copper metal complexes such as methanesulfonic acid. Most typical electrolytic copper plating baths contain copper sulphate or copper methane sulfonate in an acid solution. Thus, the concentration of copper ions and acid can vary over a wide range; for example, from about 4 to about 135 grams per liter of copper ion, preferably from about 40 to about 1000 grams per liter of copper ion, and about 2 to about 2 2 5 g / liter of acid, preferably about 10 to about 50 g / liter of acid. In one embodiment, the copper source is one of the sources of copper sulfate as the substrate, i.e., copper sulfate or copper sulfate pentahydrate. In another specific manifestation, the copper source is copper methane sulfonate. In the particular manifestation that the copper source is a sulfate-based source, the copper concentration range is typically from about 5 grams per liter to about 75 grams per liter, such as from about 5 grams per liter to about 30 grams per liter, or about 30. G/liter to about 75 g/l. Copper methane sulfonate is a more soluble source of copper, and the copper concentration range can be broader, such as from about 5 grams per liter to about 135 grams per liter, such as from about 75 grams per liter to about 135 grams per liter, or about 4 gram / liter to about -22- 200907113 100 g / liter. . In a low copper system, the copper ion concentration can range from about 5 grams per liter to about 30 grams per liter, e.g., between about 8 grams per liter to about 25 grams per liter. In some high copper systems, the concentration of copper particles may range from about 35 grams per liter to about 135 grams per liter, such as between about 35 grams per liter to about 75 grams per liter, preferably about 35 grams per liter. It is raised to about 60 g/liter, preferably about 75 g/liter to about 135 g/liter, preferably about 1 gram/liter to about 3-5 gram/liter. The acid source in the electrolytic copper plating bath includes sulfuric acid, methanesulfonic acid, phosphoric acid, acetic acid, and boric acid. The acid concentration may range from about 2 to about 225 grams per liter of acid, preferably from about 10 grams per liter to about 50 grams per liter. Chloride ions can also be used in baths at concentrations up to 200 mg/L, preferably from about 10 to 90 mg/l. Chlorine ions in these concentration ranges are added to enhance the functionality of other bath additives. These additive systems include accelerators, inhibitors, and leveling agents. A variety of additives can typically be used in the bath to provide the surface refining required for the electroplated copper metal. More than one additive is often used, and each additive forms a desired function. At least two additives are typically used to initiate the top-up charge of the interconnect features and to improve the physical properties (e.g., brightness), structural properties, and electrical properties (e.g., electrical conductivity and reliability) of the metal being plated. Use special additives (often organic additives) for particle refining, inhibit dendritic growth, and improve coverage and plating skills. A particularly desirable additive system utilizes a mixture of aromatic or aliphatic quaternary amines, polythioether compounds, and polyacids. Other additives include, for example, selenium, tellurium, and sulfur compounds. Figure 2 is a flow diagram of the method steps for preparing a wafer-to-wafer laminate or a wafer-to-wafer laminate comprising through-hole via metallization. -23-200907113 The wafer substrate (ie, the device wafer) for metallization of the electrolytic copper deposition solution of the present invention comprises a through hole and a through-through hole, which are generally known by photolithography and etching methods. preparation. In a typical method, a conventional photoresist material is applied by spin coating to the cleaned and dried surface of the device wafer. The photoresist material can be soft baked for about 5 to 30 minutes at a temperature of from about 60 ° C to about 10 ° C to remove excess solvent. After soft baking, the photoresist is exposed to ultraviolet light in a manner that defines a pattern of copper metallization. The exposed photoresist material is then dissolved using a developing solution. The wafer and photoresist material defining the copper metallization pattern are then hard baked, typically between about 20 and 30 ° C for about 20 to 30 minutes. The exposed wafer is then uranium engraved to define a via pattern in a manner known in the art, the via being then coated with a barrier layer to inhibit copper diffusion, which may be titanium nitride, giant, nitrogen Huge, or awkward. Second, the barrier layer is typically seeded with a seed layer of copper or other metal to initiate copper overplating on it. The copper seed layer may be applied by chemical vapor deposition (CVD), physical vapor deposition (PVD) or the like. The electrolytic copper deposition composition and method of the present invention is then used to electroplate a via having a barrier layer and a copper seed layer. A plating apparatus for electroplating a semiconductor substrate is known and described in, for example, U.S. Patent No. 6, 〇24,856 to Haydu et al. The electroplating apparatus includes an electrolysis plating bath that contains the deposition solution and is made of a suitable material such as plastic or other material inert to the electroplating solution. The trough can be cylindrical to provide special plating for the wafer. The cathode is disposed horizontally above the trench and may be any type of substrate such as a wafer having openings such as trenches and vias. The anode is also preferably circular for wafer electroplating and is placed horizontally below the grooves -24-200907113 to form a space between the anode and the cathode. The anode is typically a soluble electrode such as copper metal. Bath additives can be used in combination with membrane technology developed by different tool manufacturers. In this system, the anode can be separated from the organic bath additive by a membrane. The purpose of the separation of the cathode and organic bath additives is to minimize oxidation of the organic bath additive on the anode surface. The cathode substrate and the anode are wired to be electrically connected to a rectifier (power supply), respectively. The cathode substrate for direct current or pulsed current has a net negative charge such that copper ions in the solution are reduced on the cathode substrate such that plated copper metal is formed on the surface of the cathode. Furthermore, the net negative charge on the cathode attracts a net positively charged coated copper nanoparticle that will adhere to the wafer substrate. As the reduction of copper ions continues during the plating operation, the copper nanoparticles are surrounded by copper metallization established around the surface of the nanoparticles. The oxidation reaction is carried out at the anode. If periodic periodic pulse plating is used, the same oxidation reaction can be carried out at the cathode. The cathode and anode can be placed horizontally or vertically in the tank. During operation of the electroplating system, copper metal is electroplated on the surface of the cathode substrate when the rectifier is energized. Pulse current, DC, periodic reverse current, periodic pulsed reverse current, or other suitable current can be utilized. It has been found that a pulsed current of about 50 to about 1 〇〇 milliseconds (i.e., a current of 25 to 50 milliseconds is applied followed by a rest period of 25 to 50 milliseconds) produces copper deposits, and conventional DC Electroplating (which is performed from a bath of copper metallization from a bath consisting of copper ions) compared to the same plating current (as measured by total coulomb (C 〇u 1 〇mbs)) -25- 200907113 has a large quality. Therefore, pulse plating using a bath containing copper nanoparticles is used to charge the via holes in a higher plating efficiency than the conventional plating method. The current density can be up to about 1 A/dm2, typically between about 0.2 A/dm2 and about 6 A/dm2. It is preferred to use an anode to cathode ratio of about 1:1, but this ratio can also vary widely from about 1:4 to 4:1. In a preferred embodiment, the following pulse current profile is used for plating: current density 0.3 A/dm2 for 25 milliseconds, followed by a 25 millisecond break. In another preferred embodiment, the following pulse current profile is used for plating: current density 1 A/dm2 lasts 25 milliseconds, followed by a 25 millisecond break. The temperature of the electrolytic solution can be maintained using a heater/cooler whereby the electrolytic solution is removed from the holding tank and passed through the heater/cooler and then circulated to the holding tank. For example, the bath temperature is typically about room temperature (e.g., about 20-27 ° C), but can be elevated to a high temperature of about 40 ° C or higher. This method also uses a mixed solution in the electrolytic plating bath, which is supplied by agitation or preferably by recycling the electrolytic solution stream flowing through the tank. The flow through the electrolytic plating bath provides a residence time of the electrolytic solution typically less than about 1 minute in the tank, more typically a residence time of less than 30 seconds, such as a residence time of 10-20 seconds. Referring again to Figure 2. After the via fill, the wafer surface and exposed copper metallization can be cleaned by chemical mechanical polishing as is known in the art. The wafer can be thinned by conventional etching techniques to expose the copper metallization underlayer, thereby obtaining a through-via via, wherein copper metallization extends from the back side of the wafer or IC mold to the front side, that is, the activity of the wafer or mold. side. The wafers can be further processed, stacked, and singulated by methods known in the art to obtain devices comprising multiple device level layers, each of which allows -26-200907113 to be electrically connected by a through-via via. It is to be understood that the invention is not limited by the scope of the invention as defined in the appended claims. [Embodiment] The following non-limiting examples are provided to further illustrate the invention. Example 1: Coated Copper Nanoparticles Copper nanoparticles were coated with bifunctional molecules. Copper nanoparticles (200 nm average diameter) are ND copper from NanoDymanics Inc. (Buffalo, NY) and have a particle size distribution wherein at least about 80% of the nanoparticles have a particle size of about 1 〇〇. And the diameter of about 300 nanometers. The copper nanoparticles were cleaned in a solution containing concentrated acetic acid and hydrofluoric acid (5%) to remove surface oxides. The cleaned copper nanoparticles are washed in deionized distilled water. The bifunctional molecule is dodecyltrimethylammonium chloride available from Enthone Inc. (West Haven, CT) under the tradename pALLADEX ADDITIVE 1. A coating slurry was prepared by adding copper nanoparticles (5.6 g/liter) and dodecyltrimethylammonium chloride (2 ml/liter) to an aqueous solution. The solution additionally contains copper ions, sulfuric acid, and chloride ions. The coating slurry was stirred at room temperature for about 3 hours in the setting 5 of Corning Stirrer to obtain a microcapsule coating around the nanoparticles. Example 2: Electrolytic copper deposition bath containing copper nanoparticles -27- 200907113 An electrolytic copper deposition bath (bath A, total volume 2 S0 ml) containing the following components was prepared: coated copper nanoparticles (5.6 g/ Li) copper sulphate (50 g / liter); sulfuric acid (80 g / liter); chloride ion (5 〇 ppm); accelerator (10 ml / liter); inhibitor (2 ml / liter); (4 ml / liter). This bath was prepared as follows: 1. Add 250 3⁄4 liter of electrolytic copper base solution (containing 5 g/L copper ion, 80 g/L sulfuric acid and 50 ppm chloride ion) to a 400 ml beaker. 2. Using a micropipette (WHEATON 20〇-l〇〇〇pL micropipette) to add accelerator (1.2 5 ml), inhibitor (1.25 ml) and leveling agent (1.25 ml) to the beaker. 3. Add ND copper nanoparticles (ι_4g) to the beaker. 4. Stir the bath for 3 hours at room temperature. A comparative electrolytic copper deposition bath containing the following ingredients (Comparative Bath B, total volume 250 ml) was prepared: copper ion (50 g/l); sulfuric acid (8 g/l); chloride ion (50 ppm); accelerator ( 5 ml / liter); inhibitor (5 ml / liter); leveling agent (5 ml / liter). Example 3: Electrolytic copper deposition from the bath of Example 2 Baths A and B from Example 2 were used to deposit a copper layer on the Hull Cell Panel. 〇.5A current under DC or pulse current conditions (2
Amp s/dm2之電流密度）使浴被電鍍足夠之時間以產生 1 8 00庫侖。 以0.5A直流（電流密度=2A/dm2 )從浴B濺積1小時 -28 - 200907113 澱積出0.58克銅於Hull Cell Panel上。在這些條件下之 理論產率是0.5 923克。因此，從慣用浴之直流電鍍產生 9 7.9 %之電鍍效率。 在數項測試中使用包含銅奈米粒子之浴A以澱積銅於 數個板上。以下表I顯示所用之電鍍變化曲線、基板重量 之增加、及所計算之電鍍效率。The current density of Amp s/dm2) allows the bath to be plated for a sufficient time to produce 1 800 coulombs. Sputtered from bath B for 1 hour at 0.5 A DC (current density = 2 A/dm2). -28 - 200907113 0.58 g of copper was deposited on the Hull Cell Panel. The theoretical yield under these conditions is 0.5923 g. Therefore, direct plating from a conventional bath produces a plating efficiency of 97.9%. Bath A containing copper nanoparticles was used in several tests to deposit copper on several plates. Table I below shows the plating profile used, the increase in substrate weight, and the calculated plating efficiency.
表I 電鍍變化曲線 基板增加之重量(克） 電鍍效率1 0.5A,直流1小時 0.5576 94.1% 0_5A，1秒關掉,1秒打開之脈 衝電流2小時 0.5470 92.3% 0.5A, 50毫秒關掉,50毫秒 打開之脈衝電流2小時 0.5862 99.0% 0.5A, 25毫秒關掉，25毫秒 打開之脈衝電流2小時 0.6037 101.09% 註1 :藉基板增加之重量除以使用浴B之基板增加之重量以計算電鍍效率。 從表I顯見’·使用短週期之脈衝電流變化曲線增加電 鍍效率至理論限制之上，其中該理論限制是由銅金屬化來 源由銅離子組成的浴計算得到。 實例4 :從實例2之浴的電解銅澱積作用 使用來自實例2之浴A及B以澱積銅層於Hull Cell Panel上。在直流或脈衝電流狀況下以 0.5A電流（2 Amps/dm2之電流密度）使浴被電鍍足夠之時間以產生 1 8 00庫侖。 -29- 200907113 以0.5 A直流（電流密度=2A/dm2 )從浴B澱積1小時 澱積出0.5916克銅於Hull Cell Panel上。在這些條件下 之理論產率是0.5 923克。因此，從慣用浴之直流電鍍產 生9 9.9 %之電鍍效率。 在數項測試中使用包含銅奈米粒子之浴A以澱積銅於 數個板上。以下表II顯示所用之電鎪變化曲線、基板重量 之增加、及所計算之電鍍效率。Table I Electroplating curve substrate weight added (g) Plating efficiency 1 0.5A, DC 1 hour 0.5576 94.1% 0_5A, 1 second off, 1 second open pulse current 2 hours 0.5470 92.3% 0.5A, 50 ms off, 50 milliseconds open pulse current 2 hours 0.5862 99.0% 0.5A, 25 milliseconds off, 25 milliseconds open pulse current 2 hours 0.6037 101.09% Note 1: The weight added by the substrate is divided by the weight of the substrate using the bath B to calculate Plating efficiency. It is apparent from Table I that the short-period pulse current curve is used to increase the plating efficiency above the theoretical limit, which is calculated from a bath composed of copper ions from a copper metallization source. Example 4: Electrolytic copper deposition from the bath of Example 2 Baths A and B from Example 2 were used to deposit a copper layer on the Hull Cell Panel. The bath was plated at a current of 0.5 A (current density of 2 Amps/dm2) under DC or pulse current conditions for a sufficient time to produce 1 800 coulombs. -29- 200907113 0.5916 g of copper was deposited on the Hull Cell Panel by depositing 0.5 B DC (current density = 2 A/dm2) from bath B for 1 hour. The theoretical yield under these conditions is 0.5923 g. Therefore, direct electroplating from a conventional bath produces an electroplating efficiency of 99.9%. Bath A containing copper nanoparticles was used in several tests to deposit copper on several plates. Table II below shows the ename change curve used, the increase in substrate weight, and the calculated plating efficiency.
表II 電鍍變化曲線 基板增加之重量(克） 電鍍效率1 0.5A，直流1小時 0.598 101.0% 0.5A，1秒關掉，1秒打開之脈 衝電流2小時 0.593 100.1% 0.5A，50毫秒關掉，50毫秒 打開之脈衝電流2小時 0.6034 101.9% 0.5A, 25毫秒關掉，25毫秒 打開之脈衝電流2小時 0.6431 108.6% 0.5A, 25毫秒關掉，25毫秒 打開之脈衝電流2小時 (添加 2mL/L Pd WA) 0.6679 113.8% 註1 :藉基板增加之重量除以使用浴B之基板增加之重量以計算電鑛效率。 當介紹本發明之元素或其較佳具體表現時，“一 ”、‘ 此”及“該”企圖意指有一或多元素。“包含”、“包括”及“具 有”各詞企圖是總括的且意指除了所列之元素之外還有另 外的元素。 鑒於以上，將見到本發明之數項目的被達成且獲得其 他有利的結果。 因爲在以上組成物及方法中可以有不同之改變且不偏 -30- 200907113 離本發明範圍，在以上描述中所含有及在所附圖式中所m 示之所有的項目將被解釋成爲說明性的且非爲限制意_ $ 【圖式簡單說明】 圖1Α至1C是銅金屬化之直通矽通孔的照片’其說明 (A )由無缺陷底部向上塡充技術所得之完美的銅金® $ ,(Β)典型由整合（c〇nf>ormal)塡充技術所得之具有接 縫於其中之銅金屬化，及（C)典型由箍斷（pinch 〇ff) 所得之具有空隙於其中之銅金屬化。 圖2是直通矽通孔製法之流程圖。 -31 -Table II Electroplating Change Curve Substrate Increased Weight (g) Plating Efficiency 1 0.5A, DC 1 hour 0.598 101.0% 0.5A, 1 second off, 1 second open pulse current 2 hours 0.593 100.1% 0.5A, 50ms off , 50 milliseconds open pulse current 2 hours 0.6034 101.9% 0.5A, 25 milliseconds off, 25 milliseconds open pulse current 2 hours 0.6431 108.6% 0.5A, 25 milliseconds off, 25 milliseconds open pulse current 2 hours (add 2mL /L Pd WA) 0.6679 113.8% Note 1: The weight of the substrate is divided by the weight added by the substrate using Bath B to calculate the efficiency of the ore. The articles "a", "the", and "the" are intended to mean one or more of the elements of the present invention, and the meaning of "including", "including", and "having" is intended to be inclusive. And means that there are additional elements in addition to the listed elements. In view of the above, it will be seen that several items of the present invention are achieved and other advantageous results are obtained. Because there may be different changes in the above compositions and methods. All of the items contained in the above description and shown in the drawings are to be construed as illustrative and not restrictive in the scope of the present invention. Fig. 1Α to 1C are photographs of through-holes of copper metallization. The description (A) is perfect for copper gold® from the defect-free bottom up-fill technique. ( ,) is typically integrated (c〇nf> Ormal) the copper metallization obtained by the splicing technique with seams, and (C) the copper metallization obtained by the pinch 〇ff with voids therein. Figure 2 is a straight through 矽 through hole method Flow chart. -31 -
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| US9809891B2 (en) | 2014-06-30 | 2017-11-07 | Rohm And Haas Electronic Materials Llc | Plating method |
| US10512174B2 (en) | 2016-02-15 | 2019-12-17 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes to reduce voids and other defects |
| US10508357B2 (en) | 2016-02-15 | 2019-12-17 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes to reduce voids and other defects |
| US10590514B2 (en) | 2016-07-01 | 2020-03-17 | Xtalic Corporation | Nanostructured aluminum zirconium alloys for improved anodization |
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