US20210222311A1 - Plating solution and metal composite and method of manufacturing the same - Google Patents
Plating solution and metal composite and method of manufacturing the same Download PDFInfo
- Publication number
- US20210222311A1 US20210222311A1 US17/222,287 US202117222287A US2021222311A1 US 20210222311 A1 US20210222311 A1 US 20210222311A1 US 202117222287 A US202117222287 A US 202117222287A US 2021222311 A1 US2021222311 A1 US 2021222311A1
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- United States
- Prior art keywords
- fullerene
- metal
- hydrophilic
- composite material
- metal composite
- Prior art date
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- 239000002905 metal composite material Substances 0.000 title claims abstract description 40
- 238000007747 plating Methods 0.000 title abstract description 72
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000002184 metal Substances 0.000 claims abstract description 57
- 239000010949 copper Substances 0.000 claims description 31
- 125000000524 functional group Chemical group 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000002296 dynamic light scattering Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001868 water Inorganic materials 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 12
- AOITVOSSTJRHSS-UHFFFAOYSA-N (c{60}-i{h})[5,6]fullerane-1,2,3,4,5,7,13,23,24,27,29,32,35,36,39,40,42,44,49,50,53,55,56,58-tetracosol Chemical compound OC12C3C4C(O)(C56O)C7(O)C1C(C18O)(O)C9C2(O)C2C(C%10C%11(C(C%12(C(O)(C%13%14)C%15%11O)O)(O)C%11%16)O)C3C%15C4C%14C5C3C%13C(C4C5(O)C%13%14)(O)C%12C5C%11C5C%13(O)C%11C%12(O)C%13(O)C5C%16C%10(O)C2C%13(O)C9(O)C%12C8C2(O)C(C58O)C1C7C6C8(O)C3(O)C4C5C%14C2%11 AOITVOSSTJRHSS-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000009413 insulation Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 7
- 238000001819 mass spectrum Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- -1 e.g. Chemical class 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 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 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003657 tungsten Chemical class 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- AMPCGOAFZFKBGH-UHFFFAOYSA-N 4-[[4-(dimethylamino)phenyl]-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]-n,n-dimethylaniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 AMPCGOAFZFKBGH-UHFFFAOYSA-N 0.000 description 1
- QNJODRNAFXEVIC-UHFFFAOYSA-N COC.COCOC Chemical compound COC.COCOC QNJODRNAFXEVIC-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- XXACTDWGHQXLGW-UHFFFAOYSA-M Janus Green B chloride Chemical compound [Cl-].C12=CC(N(CC)CC)=CC=C2N=C2C=CC(\N=N\C=3C=CC(=CC=3)N(C)C)=CC2=[N+]1C1=CC=CC=C1 XXACTDWGHQXLGW-UHFFFAOYSA-M 0.000 description 1
- MQGLABSPPZYVCR-UHFFFAOYSA-N OC1C2(O)CC3(O)/C4=C5\C6(O)/C7=C(\C(O)C6(O)C3O)C(O)C3(O)C(O)C6(O)C(O)C8(O)C(O)C9(O)CC1(O)C1=C2C4(O)C2(O)C5(O)C4(O)C7(O)C3(O)C3(O)C6(O)C8(O)/C5=C\9C1(O)C2(O)C5(O)C43O Chemical compound OC1C2(O)CC3(O)/C4=C5\C6(O)/C7=C(\C(O)C6(O)C3O)C(O)C3(O)C(O)C6(O)C(O)C8(O)C(O)C9(O)CC1(O)C1=C2C4(O)C2(O)C5(O)C4(O)C7(O)C3(O)C3(O)C6(O)C8(O)/C5=C\9C1(O)C2(O)C5(O)C43O MQGLABSPPZYVCR-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229910020177 SiOF Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 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
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- LGLFFNDHMLKUMI-UHFFFAOYSA-N crystal violet cation Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C1C=CC(=[N+](C)C)C=C1 LGLFFNDHMLKUMI-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 108010094020 polyglycine Proteins 0.000 description 1
- 229920000232 polyglycine polymer Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NJZLKINMWXQCHI-UHFFFAOYSA-N sodium;3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound [Na].[Na].OS(=O)(=O)CCCSSCCCS(O)(=O)=O NJZLKINMWXQCHI-UHFFFAOYSA-N 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
- C01B32/156—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
-
- 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
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
-
- 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- 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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/04—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching
- H05K3/045—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching by making a conductive layer having a relief pattern, followed by abrading of the raised portions
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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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/032—Materials
- H05K2201/0323—Carbon
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09009—Substrate related
- H05K2201/09036—Recesses or grooves in insulating substrate
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
Definitions
- a plating solution, a metal composite material, and a method of manufacturing the same are disclosed.
- a method of forming the fine metal line may for example include a method of filling a metal in a groove such as a via and a trench through an electrodeposition such as electroplating a metal.
- ampacity i.e., ampere capacity
- a metal line reaches a limit according to development of information technology (IT)
- IT information technology
- ampacity is defined as an amount of current at which resistivity does not change but as the current increases beyond the ampacity, the resistivity increases.
- An embodiment provides a plating solution contributing to forming a fine pattern as well as improving ampacity.
- An embodiment provides a metal composite material contributing to forming a fine pattern as well as improving ampacity.
- an embodiment provides a method of forming the metal composite material.
- an embodiment provides a wire, a flexible printed circuit (FPC), and an electronic device which include the metal composite material.
- FPC flexible printed circuit
- the plating solution includes a metal salt, a hydrophilic fullerene, and water.
- the hydrophilic fullerene may include a hydrophilic functional group bound to a fullerene core.
- the functional group may include a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, a sulfhydryl group, a phosphate group, or a combination thereof.
- the hydrophilic fullerene may include an average of 2 to 44 functional groups bound to the fullerene core.
- the hydrophilic fullerene may include an average of 12 to 44 functional groups bound to the fullerene core.
- the hydrophilic fullerene may be represented by C x (OH) y (wherein, x is 60, 70, 74, 76, or 78 and the average value of y is 2 to 44).
- the metal salt may be selected from a copper salt, a silver salt, a gold salt, an aluminum salt, a calcium salt, a zinc salt, a tungsten salt, an iron salt, a tin salt, a platinum salt, a nickel salt, or a combination thereof.
- a metal-fullerene composite that is a reaction product of a metal cation of the metal salt and the hydrophilic fullerene may be further included.
- the plating solution may have pH of 3.5 or less.
- the hydrophilic fullerene may be present in an amount of about 10 to about 100 parts by weight based on 100 parts by weight of the metal salt.
- a metal composite material including a metal and a hydrophilic fullerene is provided.
- the hydrophilic fullerene may be chemically bonded with the metal.
- the metal may include copper, silver, gold, aluminum, calcium, zinc, tungsten, iron, tin, platinum, nickel, or a combination thereof.
- a wire includes the metal composite material.
- a flexible printed circuit includes the wire.
- an electronic device includes the wire.
- an electronic device includes the flexible printed circuit (FPC).
- FPC flexible printed circuit
- a method of forming a metal composite material includes preparing the plating solution, disposing a substrate including a metal layer or a metal plate and an opposed electrode in the plating solution, and plating a metal composite material including a hydrophilic fullerene on the metal layer or the metal plate by flowing a current between the metal layer or the metal plate and the opposed electrode to form the metal composite material.
- the plating of the metal composite material may be performed at current density of about 0.1 to about 1.0 amperes per square meter (A/m 2 ).
- FIG. 1 is a schematic view partially showing a flexible printed circuit (FPC) including a metal composite material according to an embodiment
- FIGS. 2 to 6 are schematic views showing a method of manufacturing the flexible printed circuit (FPC) of FIG. 1 ,
- FIG. 7 is a mass spectrum of a copper-fullerene composite of Example 1,
- FIG. 8 is a mass spectrum of a hydroxyl fullerene of the Synthesis Example
- FIG. 9 is a graph showing a content of fullerene (C60) included in a Cu plating layer of the Example depending on current density,
- FIG. 10 is a graph showing a content of a hydroxyl group (OH) included in the Cu plating layer of the Example depending on current density
- FIG. 11 is a schematic view showing a sample for measuring a resistivity change of each Cu plating of the Example and the Comparative Example depending on current density,
- FIG. 12 is a graph showing a resistivity change of each Cu plating layer plated at current density of 0.1 A/m 2 of the Example and the Comparative Example depending on current density, and
- FIG. 13 is a graph showing a resistivity change of each Cu plating layer plated at current density of 1.0 A/m 2 of the Example and the Comparative Example depending on current density.
- Example embodiments of the present disclosure will hereinafter be described in detail, and may be easily performed by a person having an ordinary skill in the related art. However, actually applied structures may be embodied in many different forms, and is not to be construed as limited to the example embodiments set forth herein.
- “About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ⁇ 30%, 20%, 10% or 5% of the stated value.
- Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
- a plating solution according to an embodiment includes a metal salt and a hydrophilic fullerene.
- the metal salt is a compound including, e.g., consisting of, metal cations and anions, and may be reduced to a low resistance metal, for example, a metal having conductivity of greater than or equal to about 1 ⁇ 10 7 siemens per meter (S/m).
- the metal salt may be for example a copper salt, a tungsten salt, an iron salt, a tin salt, a platinum salt, a nickel salt, or a combination thereof, but is not limited thereto.
- the metal salt may be a copper salt, for example copper sulfate (CuSO 4 .5H 2 O), copper acetate (Cu(CH 3 COO) 2 .H 2 O), copper nitrate (Cu(NO 3 ) 2 ), copper formate (Cu(HCOO) 2 ), copper chloride (CuCl 2 .H 2 O), copper cyanide (CuCN), or a combination thereof, but is not limited thereto.
- the metal salt may be included in an amount supplying metal cations in a sufficient amount for electroplating, for example, in an amount of about 0.05 weight percent (wt %) to about 1 wt % based on that of a plating solution. Within the range, the metal salt may be included in an amount of about 0.07 wt % to about 0.8 wt %, about 0.1 wt % to about 0.5 wt %, or about 0.1 wt % to about 0.3 wt %.
- the hydrophilic fullerene may be a compound including a hydrophilic functional group bound to the fullerene core.
- the fullerene core in general may be hydrophobic but is linked with a hydrophilic functional group and thus may become hydrophilic.
- the fullerene core may be for example C60, C70, C74, C76, or C78 but is not limited thereto.
- the hydrophilic functional group may be for example a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, sulfhydryl group, a phosphate group, or a combination thereof, but is not limited thereto.
- the hydrophilic fullerene may include an average of greater than or equal to about two hydrophilic functional groups per one fullerene core, for example an average of about 2 to about 44 hydrophilic functional groups, for example, an average of about 8 to about 44 hydrophilic functional groups, for example, an average of about 12 to about 44 hydrophilic functional groups, for example, an average of about 24 to about 44 hydrophilic functional groups, for example, an average of about 24 to about 40 hydrophilic functional groups, and for example an average of about 24 to about 36 hydrophilic functional groups.
- the hydrophilic fullerene may be a hydroxyl fullerene and may be, for example represented by C x (OH) y (wherein, x is 60, 70, 74, 76, or 78, and an average value of y is about 2 to about 44).
- the hydrophilic fullerene may be included in an amount of about 10 to about 100 parts by weight based on 100 parts by weight of the metal salt. Within the range, it may be included in an amount of about 15 to about 100 parts by weight, for example about 15 to about 80 parts by weight, about 15 to about 70 parts by weight, about 15 to about 60 parts by weight, about 15 to about 50 parts by weight, about 15 to about 40 parts by weight, or about 15 to about 30 parts by weight.
- the plating solution may further include a metal-fullerene composite of a metal cation of the metal salt and the hydrophilic fullerene.
- the metal-fullerene composite is a reaction product obtained through a reaction of a metal cation of the metal salt and a functional group of the hydrophilic fullerene in the plating solution, and the metal cation and the hydrophilic fullerene may have a chemical bond, e.g., the metal cation and the hydrophilic fullerene may be chemical bonded to one another.
- the reaction may be for example performed by mixing the metal salt and the hydrophilic fullerene, for example, at room temperature (about 25° C.).
- the metal-fullerene composite may be for example represented by Chemical Formula A or B.
- x is 60, 70, 74, 76, or 78, and an average value of y is about 2 to about 44.
- the plating solution including a metal-fullerene composite may have a different color from a plating solution including a metal salt, for example, a plating solution including a copper slat may be blue, but a plating solution including a copper-fullerene composite may be blackish brown or black.
- a particle diameter of the metal-fullerene composite may be measured through dynamic light scattering (DLS) and, for example, less than or equal to about 10 nanometers (nm), less than or equal to about 8 nm, less than or equal to about 7 nm, or less than or equal to about 5 nm.
- the particle diameter of the metal-fullerene composite may be, for example, about 1 nm to about 10 nm, about 1 nm to about 8 nm, about 1 nm to about 7 nm, or about 1 nm to about 5 nm.
- the plating solution may further include acid.
- the acid may be for example sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), acetic acid (CH 3 COOH), fluoroboric acid (HBF 4 ), a C1-C6 alkyl)sulfonic acid, a C6-C18 aryl)sulfonic acid, phosphoric acid, or a combination thereof, but is not limited thereto.
- the acid may be included in an amount of about 0.01 to about 10 wt % based on the plating solution. Within the range, it may be included in an amount of about 0.01 to about 8 wt %, about 0.01 to about 7 wt %, about 0.01 to about 5 wt %, or about 0.01 to about 3 wt %.
- the plating solution may include for example a leveler, a suppressor, a promoter (catalyst), a gloss auxiliary agent (brightener), a reducing agent, and/or various additives.
- the leveler may include polyethylene imine or a derivative thereof, quaternized polyethylene imine, polyglycine, poly(allylamine), polyaniline, polyurea, polyacrylamide, poly(melamine-co-formaldehyde), a reaction product of an amine and epichlorohydrin, a reaction product of an amine, epichlorohydrin, and polyalkylene oxide, a reaction product of an amine, polyepoxide, polyvinylpyridine, polyvinylimidazole, polyvinylpyrrolidone, or a copolymer thereof, nigrosine, pentamethyl-para-rosaniline hydrohalide, hexamethyl-para-rosaniline hydrohalide, trialkanolamine or a derivative thereof, a compound having a functional group of Chemical Formula N—R—S (wherein, R is substituted alkyl, unsubstituted alkyl, substituted aryl, or unsubstituted aryl), or a combination
- the suppressor may be for example a polymeric material, for example, a polyethylene glycol copolymer and/or a polyethylene glycol polypropylene glycol copolymer, but is not limited thereto.
- the promoter may include a sulfur-containing compound, sulfonic acid, phosphonic acid, or a salt thereof, but is not limited thereto.
- the components are independently included, for example, in a small amount of about 1 parts per million (ppm) to about 100,000 ppm.
- the plating solution may further include a solvent capable of dissolving or dispersing the aforementioned components, and the solvent may be, for example, water.
- the water may be any water such as distilled water and/or deionized water.
- the plating solution may be acidic and, for example, has a pH of 3.5 or less and thus strongly acidic.
- the plating solution may have, for example, a pH of 3.0 or less, for example, a pH of 2.5 or less, or, for example, a pH of 2.0 or less.
- the aforementioned plating solution may be formed into a metal composite material through electroplating.
- the metal composite material may have a structure including a hydrophilic fullerene in a metal matrix, and herein, the hydrophilic fullerene may have a chemical bond with a metal, e.g., the hydrophilic fullerene may be chemical bonded to a metal.
- the metal may be, for example, copper, silver, gold, aluminum, calcium, zinc, tungsten, iron, tin, platinum, nickel, or a combination thereof, but is not limited thereto.
- an amount of the hydrophilic fullerene may be adjusted depending on a plating solution and a plating condition and, for example, the amount of the hydrophilic fullerene may be increased, as pH of the plating solution is increased, for example, as current density of plating is increased.
- the metal composite material may be effectively suppressed from electromigration, compared with a pure metal including no hydrophilic fullerene.
- Electromigration denotes a phenomenon that metal atoms are diffused in one direction along with motion of electrons and may cause a void and thus a short circuit.
- the metal composite material is suppressed from migration of metal atoms due to generation of a relatively strong electronic interaction between a hydrophilic fullerene and a metal, and on the other hand, the fullerene having a stable structure absorbs vibration energy generated by heat or a current and reduces vibration of the metal atoms and thus suppresses electromigration.
- the metal composite material may have greater ampacity than that of a pure metal including no hydrophilic fullerene.
- the ampacity denotes maximum current-carrying capacity, and the metal composite material has greater current-transport capability than that of the pure metal.
- the metal composite material may have, for example, greater than or equal to about 1.5 times or for example, greater than or equal to about twice an ampacity of the pure metal.
- the metal composite material may have equivalent or greater ampacity than that of the pure metal including no hydrophilic fullerene.
- the metal composite material may have greater than or equal to about 1.5 times a maximum current-carrying capacity of the pure metal.
- the metal composite material may be formed by using a plating solution including a hydrophilic fullerene, and during the plating, a spherical hydrophilic fullerene and/or a metal-fullerene composite having a diameter of less than or equal to a nanometer may effectively go in and fill a groove of a fine line width. Accordingly, a wire having a fine line width without a void may be effectively formed.
- the metal composite material may be used as a wire, and the wire may be, for example, included in a flexible printed circuit (FPC).
- the metal composite material may be effectively used for a wire having a fine line width, for example, a fine wire having a pitch of less than or equal to about 20 nm.
- the wire and/or flexible printed circuit may be included in various electronic devices such as a semiconductor device, a display device, and the like.
- FIG. 1 is a schematic view showing a part of a flexible printed circuit (FPC) including the metal composite material according to an embodiment.
- FPC flexible printed circuit
- the flexible printed circuit includes a substrate 10 , an insulation layer 11 , a conductive layer 12 , and a plating layer 13 .
- the substrate 10 may be an insulation substrate, a metal plate, or a silicon wafer, but is not limited thereto.
- the insulation layer 11 may include for example an inorganic material such as a SiO 2 -based insulating material such as tetraethoxysilane and the like, a SiOF-based insulating material, and a SiOC-based insulating material; an organic/inorganic material such as a hydrogen-containing polysiloxane-based insulating material and a methyl-containing polysiloxane-based insulating material; an organic material such as a polyimide-based insulating material, parylene, and Teflon; an air gap, and the like but is not limited thereto.
- the insulation layer 11 may have an alternatively embossed and depressed pattern.
- the conductive layer 12 is formed to be thin along the surface of the insulation layer 11 and may be a diffusion barrier or an electricity-feeding layer.
- the conductive layer 12 may, for example, include Ta, TaN, or a combination thereof but is not limited thereto.
- the plating layer 13 may be charged in a depressed region, that is, a groove of the insulation layer 11 and include the above metal composite material and be formed through electroplating.
- FIGS. 2 to 6 are schematic views showing a method of manufacturing the flexible printed circuit (FPC) of FIG. 1 .
- the insulation layer 11 is formed on the substrate 10 .
- the insulation layer 11 may be, for example, formed in a deposition method such as chemical vapor deposition (CVD) or in a solution process such as spin coating but is not limited thereto.
- a plurality of grooves 11 a is formed in the insulation layer 11 .
- the grooves 11 a may have a line width of less than or equal to about 20 nm.
- the grooves 11 a may be formed through photolithography but is not limited thereto.
- the conductive layer 12 is formed on the insulation layer 11 having the grooves 11 a .
- the conductive layer 12 may be, for example, formed through a physical vapor deposition such as sputtering but is not limited thereto.
- the substrate 10 and the opposed, e.g., opposing, electrode 30 are disposed in the plating solution 20 , and electroplating is performed by flowing a current between the conductive layer 12 and an opposed electrode 30 .
- current density may be about 0.1 to about 1.0 A/m 2 but is not limited thereto.
- a spherical hydrophilic fullerene and/or a metal-fullerene composite 13 a having a diameter of less than or equal to several nanometers effectively goes in the fine grooves 11 a having a line width of less than or equal to about 20 nm and charge the grooves 11 a and thus may effectively form a metal line having a fine line width.
- the plating layer 13 is formed on the conductive layer 12 .
- the plating layer 13 is formed by planarizing the plating layer 30 and filling it in the grooves 11 a.
- n denotes the number of OH at a maximum peak on a mass spectrum (LCMS) of FIGS. 7 and 8 and is marked as an integral by rounding off to the nearest whole number.
- the hydroxyl fullerenes When measured in a dynamic light scattering method (SUPTEK Yag Keceleri San. ve Tic. A.S.), the hydroxyl fullerenes have an average particle diameter of about 1 nanometer (nm).
- each plating solution of Preparation Examples 1-3 and Comparative Example 1 is prepared.
- the components other than hydroxyl fullerene and H 2 SO 4 are first mixed and then, mixed with the hydroxyl fullerene and H 2 SO 4 .
- Example 1 Hydroxyl fullerene 19.5 grams 19.5 g/L 19.5 g/L — (C 60 (OH) 24-36 , per liter (g/L) Peak: C 60 (OH) 31 C 60 (OH) 6-12 — — — — — C 60 — — — — polyacrylic acid 1 g/L 1 g/L 1 g/L 1 g/L CuSO 4 •5H 2 O 60 g/L 60 g/L 60 g/L 60 g/L H 2 SO 4 0 0 0 182 g/L NaCl 0.08 g/L 0.08 g/L 0.08 g/L 0.08 g/L SPS 0.002 g/L 0.002 g/L 0.002 g/L 0.002 g/L JGB 0.01 g/L 0.01 g/L 0.01 g/L 0.01 g/L pH 0.0
- Each of Ru/Ta is subsequently coated with a thickness of 10 nm on a silicon wafer, the silicon wafer (a cathode) and an opposed electrode (a positive electrode) are disposed to face each other in the plating solution according to Preparation Example 3, and then, the plating solution is stirred at 20° C. While the plating solution is stirred, the positive electrode and the cathode are connected to power and then, plated by flowing a current with various average current densities (0.1 amperes per square decimeter (A/dm 2 ) to about 1.0 A/dm 2 ) for 45 minutes.
- the obtained Cu plating layer (including a metal composite material) has a thickness of 1 micrometer ( ⁇ m).
- a pure Cu plating layer is obtained according to the same method as Example except for using the plating solution according to Comparative Preparation Example 1 instead of the plating solution according to Preparation Example 3.
- the evaluation is performed through a mass spectrum.
- FIG. 7 shows a mass spectrum of the copper-fullerene composite of the Example
- FIG. 8 shows a mass spectrum of the hydroxyl fullerene of the Synthesis Example.
- a content of fullerene (C60) and a hydroxyl group (OH) present in the Cu plating layer (including a metal composite material) of the Example depending on current density is examined.
- FIG. 9 is a graph showing a content of the fullerene (C60) of the Cu plating layer of the Example depending on a current density
- FIG. 10 is a graph showing a content of hydroxyl group (OH) of the Cu plating layer of the Example depending on a current density.
- contents of the fullerene (C60) and a hydroxyl group (OH) in the Cu plating layer vary depending on pH and a current density, for example, as the pH is increased, the contents of the fullerene (C60) and the hydroxyl group (OH) are increased in the Cu plating layer, and as the current density is increased, the contents of the fullerene (C60) and the hydroxyl group (OH) are increased in the Cu plating layer.
- the contents of the fullerene and the hydroxy group in the Cu plating layer may be adjusted by controlling a condition of the plating.
- the resistivity change depending on a current density is measured with N5765A made by Agilent Technologies after forming each wire (a length: 30 ⁇ m, a width: 10 ⁇ m) by using the Cu plating layers of the Example and the Comparative Example as shown in FIG. 11 .
- FIG. 12 is a graph showing a resistivity change of the Cu plating layers plated at a current density of 0.1 A/m 2 of the Example and the Comparative Example
- FIG. 13 is a graph showing a resistivity change of the Cu plating layers plated at a current density of 1.0 A/m 2 of the Example and the Comparative Example.
- the Cu plating layer of the Example shows a small resistivity change compared with that of the Cu plating layer of the Comparative Example. Accordingly, the Cu plating layer of the Example shows high electrical stability compared with that of the Cu plating layer of the Comparative Example.
- the ampacity is defined as a current capacity having resistivity (Dr/r 0 ) of greater than 1 and the resistivity increases as the current increases beyond the ampacity.
- the Cu plating layer of the Example shows greater, for example, twice, an ampacity of the Comparative Example.
Abstract
Description
- This application is a divisional application of application Ser. No. 16/176,332, filed Oct. 31, 2018, which claims priority to and the benefit of Korean Patent Application No. 10-2018-0009925 filed in the Korean Intellectual Property Office on Jan. 26, 2018, and all the benefits accruing therefrom under 35 U.S.C. § 119, the entire contents of which are incorporated herein by reference.
- A plating solution, a metal composite material, and a method of manufacturing the same are disclosed.
- Recently, research on a material and a method of forming a fine metal line has been made in accordance with reductions in sizes of electronic devices and thereby, miniaturizing an integrated circuit. A method of forming the fine metal line may for example include a method of filling a metal in a groove such as a via and a trench through an electrodeposition such as electroplating a metal.
- However, as ampacity, i.e., ampere capacity, of a metal line reaches a limit according to development of information technology (IT), development of a wire material having high ampacity is required. Herein, ampacity is defined as an amount of current at which resistivity does not change but as the current increases beyond the ampacity, the resistivity increases.
- An embodiment provides a plating solution contributing to forming a fine pattern as well as improving ampacity.
- An embodiment provides a metal composite material contributing to forming a fine pattern as well as improving ampacity.
- In addition, an embodiment provides a method of forming the metal composite material.
- Furthermore, an embodiment provides a wire, a flexible printed circuit (FPC), and an electronic device which include the metal composite material.
- According to an embodiment, the plating solution includes a metal salt, a hydrophilic fullerene, and water.
- The hydrophilic fullerene may include a hydrophilic functional group bound to a fullerene core. The functional group may include a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, a sulfhydryl group, a phosphate group, or a combination thereof.
- The hydrophilic fullerene may include an average of 2 to 44 functional groups bound to the fullerene core.
- The hydrophilic fullerene may include an average of 12 to 44 functional groups bound to the fullerene core.
- The hydrophilic fullerene may be represented by Cx(OH)y (wherein, x is 60, 70, 74, 76, or 78 and the average value of y is 2 to 44).
- The metal salt may be selected from a copper salt, a silver salt, a gold salt, an aluminum salt, a calcium salt, a zinc salt, a tungsten salt, an iron salt, a tin salt, a platinum salt, a nickel salt, or a combination thereof.
- A metal-fullerene composite that is a reaction product of a metal cation of the metal salt and the hydrophilic fullerene may be further included.
- The plating solution may have pH of 3.5 or less.
- The hydrophilic fullerene may be present in an amount of about 10 to about 100 parts by weight based on 100 parts by weight of the metal salt.
- According to an embodiment, a metal composite material including a metal and a hydrophilic fullerene is provided.
- The hydrophilic fullerene may be chemically bonded with the metal.
- The metal may include copper, silver, gold, aluminum, calcium, zinc, tungsten, iron, tin, platinum, nickel, or a combination thereof.
- According to an embodiment, a wire includes the metal composite material.
- According to an embodiment, a flexible printed circuit (FPC) includes the wire.
- According to an embodiment, an electronic device includes the wire.
- According to an embodiment, an electronic device includes the flexible printed circuit (FPC).
- According to an embodiment, a method of forming a metal composite material includes preparing the plating solution, disposing a substrate including a metal layer or a metal plate and an opposed electrode in the plating solution, and plating a metal composite material including a hydrophilic fullerene on the metal layer or the metal plate by flowing a current between the metal layer or the metal plate and the opposed electrode to form the metal composite material.
- The plating of the metal composite material may be performed at current density of about 0.1 to about 1.0 amperes per square meter (A/m2).
- Current capacity, conductivity, and electrical stability may not only be improved, but a fine pattern may also be effectively formed.
-
FIG. 1 is a schematic view partially showing a flexible printed circuit (FPC) including a metal composite material according to an embodiment, -
FIGS. 2 to 6 are schematic views showing a method of manufacturing the flexible printed circuit (FPC) ofFIG. 1 , -
FIG. 7 is a mass spectrum of a copper-fullerene composite of Example 1, -
FIG. 8 is a mass spectrum of a hydroxyl fullerene of the Synthesis Example, -
FIG. 9 is a graph showing a content of fullerene (C60) included in a Cu plating layer of the Example depending on current density, -
FIG. 10 is a graph showing a content of a hydroxyl group (OH) included in the Cu plating layer of the Example depending on current density, -
FIG. 11 is a schematic view showing a sample for measuring a resistivity change of each Cu plating of the Example and the Comparative Example depending on current density, -
FIG. 12 is a graph showing a resistivity change of each Cu plating layer plated at current density of 0.1 A/m2 of the Example and the Comparative Example depending on current density, and -
FIG. 13 is a graph showing a resistivity change of each Cu plating layer plated at current density of 1.0 A/m2 of the Example and the Comparative Example depending on current density. - Example embodiments of the present disclosure will hereinafter be described in detail, and may be easily performed by a person having an ordinary skill in the related art. However, actually applied structures may be embodied in many different forms, and is not to be construed as limited to the example embodiments set forth herein.
- In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. Like reference numerals designate like elements throughout the specification. It will be understood that when an element such as a layer, film, region, or substrate is referred to as being “on” another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
- The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms, including “at least one,” unless the content clearly indicates otherwise. “At least one” is not to be construed as limiting “a” or “an.” “Or” means “and/or.” As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
- “About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10% or 5% of the stated value.
- Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
- Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
- Hereinafter, a plating solution according to an embodiment is described.
- A plating solution according to an embodiment includes a metal salt and a hydrophilic fullerene.
- The metal salt is a compound including, e.g., consisting of, metal cations and anions, and may be reduced to a low resistance metal, for example, a metal having conductivity of greater than or equal to about 1×107 siemens per meter (S/m).
- The metal salt may be for example a copper salt, a tungsten salt, an iron salt, a tin salt, a platinum salt, a nickel salt, or a combination thereof, but is not limited thereto. For example, the metal salt may be a copper salt, for example copper sulfate (CuSO4.5H2O), copper acetate (Cu(CH3COO)2.H2O), copper nitrate (Cu(NO3)2), copper formate (Cu(HCOO)2), copper chloride (CuCl2.H2O), copper cyanide (CuCN), or a combination thereof, but is not limited thereto.
- The metal salt may be included in an amount supplying metal cations in a sufficient amount for electroplating, for example, in an amount of about 0.05 weight percent (wt %) to about 1 wt % based on that of a plating solution. Within the range, the metal salt may be included in an amount of about 0.07 wt % to about 0.8 wt %, about 0.1 wt % to about 0.5 wt %, or about 0.1 wt % to about 0.3 wt %.
- The hydrophilic fullerene may be a compound including a hydrophilic functional group bound to the fullerene core.
- The fullerene core in general may be hydrophobic but is linked with a hydrophilic functional group and thus may become hydrophilic.
- The fullerene core may be for example C60, C70, C74, C76, or C78 but is not limited thereto.
- The hydrophilic functional group may be for example a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, sulfhydryl group, a phosphate group, or a combination thereof, but is not limited thereto.
- The hydrophilic fullerene may include an average of greater than or equal to about two hydrophilic functional groups per one fullerene core, for example an average of about 2 to about 44 hydrophilic functional groups, for example, an average of about 8 to about 44 hydrophilic functional groups, for example, an average of about 12 to about 44 hydrophilic functional groups, for example, an average of about 24 to about 44 hydrophilic functional groups, for example, an average of about 24 to about 40 hydrophilic functional groups, and for example an average of about 24 to about 36 hydrophilic functional groups.
- For example, the hydrophilic fullerene may be a hydroxyl fullerene and may be, for example represented by Cx(OH)y (wherein, x is 60, 70, 74, 76, or 78, and an average value of y is about 2 to about 44).
- The hydrophilic fullerene may be included in an amount of about 10 to about 100 parts by weight based on 100 parts by weight of the metal salt. Within the range, it may be included in an amount of about 15 to about 100 parts by weight, for example about 15 to about 80 parts by weight, about 15 to about 70 parts by weight, about 15 to about 60 parts by weight, about 15 to about 50 parts by weight, about 15 to about 40 parts by weight, or about 15 to about 30 parts by weight.
- The plating solution may further include a metal-fullerene composite of a metal cation of the metal salt and the hydrophilic fullerene. The metal-fullerene composite is a reaction product obtained through a reaction of a metal cation of the metal salt and a functional group of the hydrophilic fullerene in the plating solution, and the metal cation and the hydrophilic fullerene may have a chemical bond, e.g., the metal cation and the hydrophilic fullerene may be chemical bonded to one another. The reaction may be for example performed by mixing the metal salt and the hydrophilic fullerene, for example, at room temperature (about 25° C.).
- For example, when the metal is expressed by M and an example of the hydrophilic fullerene is a hydroxyl fullerene represented by Cx(OH)y, the metal-fullerene composite may be for example represented by Chemical Formula A or B.
- In Chemical Formula A or B, x is 60, 70, 74, 76, or 78, and an average value of y is about 2 to about 44.
- For example, the plating solution including a metal-fullerene composite may have a different color from a plating solution including a metal salt, for example, a plating solution including a copper slat may be blue, but a plating solution including a copper-fullerene composite may be blackish brown or black.
- A particle diameter of the metal-fullerene composite may be measured through dynamic light scattering (DLS) and, for example, less than or equal to about 10 nanometers (nm), less than or equal to about 8 nm, less than or equal to about 7 nm, or less than or equal to about 5 nm. The particle diameter of the metal-fullerene composite may be, for example, about 1 nm to about 10 nm, about 1 nm to about 8 nm, about 1 nm to about 7 nm, or about 1 nm to about 5 nm.
- The plating solution may further include acid. The acid may be for example sulfuric acid (H2SO4), hydrochloric acid (HCl), acetic acid (CH3COOH), fluoroboric acid (HBF4), a C1-C6 alkyl)sulfonic acid, a C6-C18 aryl)sulfonic acid, phosphoric acid, or a combination thereof, but is not limited thereto.
- The acid may be included in an amount of about 0.01 to about 10 wt % based on the plating solution. Within the range, it may be included in an amount of about 0.01 to about 8 wt %, about 0.01 to about 7 wt %, about 0.01 to about 5 wt %, or about 0.01 to about 3 wt %.
- The plating solution may include for example a leveler, a suppressor, a promoter (catalyst), a gloss auxiliary agent (brightener), a reducing agent, and/or various additives.
- The leveler may include polyethylene imine or a derivative thereof, quaternized polyethylene imine, polyglycine, poly(allylamine), polyaniline, polyurea, polyacrylamide, poly(melamine-co-formaldehyde), a reaction product of an amine and epichlorohydrin, a reaction product of an amine, epichlorohydrin, and polyalkylene oxide, a reaction product of an amine, polyepoxide, polyvinylpyridine, polyvinylimidazole, polyvinylpyrrolidone, or a copolymer thereof, nigrosine, pentamethyl-para-rosaniline hydrohalide, hexamethyl-para-rosaniline hydrohalide, trialkanolamine or a derivative thereof, a compound having a functional group of Chemical Formula N—R—S (wherein, R is substituted alkyl, unsubstituted alkyl, substituted aryl, or unsubstituted aryl), or a combination thereof, but is not limited thereto.
- The suppressor may be for example a polymeric material, for example, a polyethylene glycol copolymer and/or a polyethylene glycol polypropylene glycol copolymer, but is not limited thereto.
- The promoter may include a sulfur-containing compound, sulfonic acid, phosphonic acid, or a salt thereof, but is not limited thereto.
- The components are independently included, for example, in a small amount of about 1 parts per million (ppm) to about 100,000 ppm.
- The plating solution may further include a solvent capable of dissolving or dispersing the aforementioned components, and the solvent may be, for example, water. The water may be any water such as distilled water and/or deionized water.
- The plating solution may be acidic and, for example, has a pH of 3.5 or less and thus strongly acidic. The plating solution may have, for example, a pH of 3.0 or less, for example, a pH of 2.5 or less, or, for example, a pH of 2.0 or less.
- The aforementioned plating solution may be formed into a metal composite material through electroplating.
- The metal composite material may have a structure including a hydrophilic fullerene in a metal matrix, and herein, the hydrophilic fullerene may have a chemical bond with a metal, e.g., the hydrophilic fullerene may be chemical bonded to a metal. As described above, the metal may be, for example, copper, silver, gold, aluminum, calcium, zinc, tungsten, iron, tin, platinum, nickel, or a combination thereof, but is not limited thereto.
- In the metal composite material, an amount of the hydrophilic fullerene may be adjusted depending on a plating solution and a plating condition and, for example, the amount of the hydrophilic fullerene may be increased, as pH of the plating solution is increased, for example, as current density of plating is increased.
- The metal composite material may be effectively suppressed from electromigration, compared with a pure metal including no hydrophilic fullerene. Electromigration denotes a phenomenon that metal atoms are diffused in one direction along with motion of electrons and may cause a void and thus a short circuit. Without being bound by any particular theory, the metal composite material is suppressed from migration of metal atoms due to generation of a relatively strong electronic interaction between a hydrophilic fullerene and a metal, and on the other hand, the fullerene having a stable structure absorbs vibration energy generated by heat or a current and reduces vibration of the metal atoms and thus suppresses electromigration.
- The metal composite material may have greater ampacity than that of a pure metal including no hydrophilic fullerene. The ampacity denotes maximum current-carrying capacity, and the metal composite material has greater current-transport capability than that of the pure metal. The metal composite material may have, for example, greater than or equal to about 1.5 times or for example, greater than or equal to about twice an ampacity of the pure metal.
- In this way, the metal composite material may have equivalent or greater ampacity than that of the pure metal including no hydrophilic fullerene. For example, the metal composite material may have greater than or equal to about 1.5 times a maximum current-carrying capacity of the pure metal.
- As described above, the metal composite material may be formed by using a plating solution including a hydrophilic fullerene, and during the plating, a spherical hydrophilic fullerene and/or a metal-fullerene composite having a diameter of less than or equal to a nanometer may effectively go in and fill a groove of a fine line width. Accordingly, a wire having a fine line width without a void may be effectively formed.
- The metal composite material may be used as a wire, and the wire may be, for example, included in a flexible printed circuit (FPC). The metal composite material may be effectively used for a wire having a fine line width, for example, a fine wire having a pitch of less than or equal to about 20 nm.
- The wire and/or flexible printed circuit (FPC) may be included in various electronic devices such as a semiconductor device, a display device, and the like.
-
FIG. 1 is a schematic view showing a part of a flexible printed circuit (FPC) including the metal composite material according to an embodiment. - Referring to
FIG. 1 , the flexible printed circuit (FPC) includes asubstrate 10, aninsulation layer 11, aconductive layer 12, and aplating layer 13. - The
substrate 10 may be an insulation substrate, a metal plate, or a silicon wafer, but is not limited thereto. - The
insulation layer 11 may include for example an inorganic material such as a SiO2-based insulating material such as tetraethoxysilane and the like, a SiOF-based insulating material, and a SiOC-based insulating material; an organic/inorganic material such as a hydrogen-containing polysiloxane-based insulating material and a methyl-containing polysiloxane-based insulating material; an organic material such as a polyimide-based insulating material, parylene, and Teflon; an air gap, and the like but is not limited thereto. Theinsulation layer 11 may have an alternatively embossed and depressed pattern. - The
conductive layer 12 is formed to be thin along the surface of theinsulation layer 11 and may be a diffusion barrier or an electricity-feeding layer. Theconductive layer 12 may, for example, include Ta, TaN, or a combination thereof but is not limited thereto. - The
plating layer 13 may be charged in a depressed region, that is, a groove of theinsulation layer 11 and include the above metal composite material and be formed through electroplating. -
FIGS. 2 to 6 are schematic views showing a method of manufacturing the flexible printed circuit (FPC) ofFIG. 1 . - Referring to
FIG. 2 , theinsulation layer 11 is formed on thesubstrate 10. Theinsulation layer 11 may be, for example, formed in a deposition method such as chemical vapor deposition (CVD) or in a solution process such as spin coating but is not limited thereto. - Referring to
FIG. 3 , a plurality ofgrooves 11 a is formed in theinsulation layer 11. Thegrooves 11 a may have a line width of less than or equal to about 20 nm. Thegrooves 11 a may be formed through photolithography but is not limited thereto. - Referring to
FIG. 4 , theconductive layer 12 is formed on theinsulation layer 11 having thegrooves 11 a. Theconductive layer 12 may be, for example, formed through a physical vapor deposition such as sputtering but is not limited thereto. - Referring to
FIG. 5 , thesubstrate 10 and the opposed, e.g., opposing,electrode 30 are disposed in theplating solution 20, and electroplating is performed by flowing a current between theconductive layer 12 and anopposed electrode 30. Herein, current density may be about 0.1 to about 1.0 A/m2 but is not limited thereto. - Herein, a spherical hydrophilic fullerene and/or a metal-
fullerene composite 13 a having a diameter of less than or equal to several nanometers effectively goes in thefine grooves 11 a having a line width of less than or equal to about 20 nm and charge thegrooves 11 a and thus may effectively form a metal line having a fine line width. - Referring to
FIG. 6 , theplating layer 13 is formed on theconductive layer 12. - Referring to
FIG. 1 , theplating layer 13 is formed by planarizing theplating layer 30 and filling it in thegrooves 11 a. - Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, these examples are exemplary, and the present disclosure is not limited thereto.
- 10 grams (g) of a hydroxyl fullerene precursor (C60(OH)6-12, Nanom Spectra D100, Frontier Carbon Corp.) is dispersed in a 30% hydrogen peroxide solution and then, stirred at 60° C. for 48 hours in a flask to synthesize a hydroxyl fullerene represented by Chemical Formula 1 (C60(OH)24-36, Peak: C60(OH)31. In C60(OH)n (Peak), n denotes the number of OH at a maximum peak on a mass spectrum (LCMS) of
FIGS. 7 and 8 and is marked as an integral by rounding off to the nearest whole number. - When measured in a dynamic light scattering method (SUPTEK Yag Keceleri San. ve Tic. A.S.), the hydroxyl fullerenes have an average particle diameter of about 1 nanometer (nm).
- As shown in Table 1, each plating solution of Preparation Examples 1-3 and Comparative Example 1 is prepared. When the plating solution is prepared, the components other than hydroxyl fullerene and H2SO4 are first mixed and then, mixed with the hydroxyl fullerene and H2SO4.
-
TABLE 1 Comparative Preparation Preparation Preparation Preparation Example 1 Example 2 Example 3 Example 1 Hydroxyl fullerene 19.5 grams 19.5 g/L 19.5 g/L — (C60(OH)24-36, per liter (g/L) Peak: C60(OH)31 C60(OH)6-12 — — — — C60 — — — — polyacrylic acid 1 g/L 1 g/L 1 g/L 1 g/L CuSO4•5H2O 60 g/L 60 g/L 60 g/L 60 g/L H2SO4 0 0 0 182 g/L NaCl 0.08 g/L 0.08 g/L 0.08 g/L 0.08 g/L SPS 0.002 g/L 0.002 g/L 0.002 g/L 0.002 g/L JGB 0.01 g/L 0.01 g/L 0.01 g/L 0.01 g/L pH 0.0 1.0 2.0 0.0 -
- C60(OH)6-12, Nanom Spectra D100, Frontier Carbon Corp.
- C60: NANOM SPECTRA D100: Frontier Carbon Corp.
- polyacrylic acid: Wako Pure Chemical Industries, Ltd.
- CuSO4.5H2O: Kanto Chemical Co., Inc.
- SPS: 3,3′-dithiobis(1-propanesulfonic acid) disodium: Tokyo Chemical Industry Co., Ltd.
- JGB: Janus Green B: Tokyo Chemical Industry Co., Ltd.
- pH: pH Meter SP-2100 (Yag Keceleri San. ve Tic. A.S.)
- Each of Ru/Ta is subsequently coated with a thickness of 10 nm on a silicon wafer, the silicon wafer (a cathode) and an opposed electrode (a positive electrode) are disposed to face each other in the plating solution according to Preparation Example 3, and then, the plating solution is stirred at 20° C. While the plating solution is stirred, the positive electrode and the cathode are connected to power and then, plated by flowing a current with various average current densities (0.1 amperes per square decimeter (A/dm2) to about 1.0 A/dm2) for 45 minutes. The obtained Cu plating layer (including a metal composite material) has a thickness of 1 micrometer (μm).
- A pure Cu plating layer is obtained according to the same method as Example except for using the plating solution according to Comparative Preparation Example 1 instead of the plating solution according to Preparation Example 3.
- Whether or not hydroxyl fullerene is included in the Cu plating layer of the Example is evaluated.
- The evaluation is performed through a mass spectrum.
-
FIG. 7 shows a mass spectrum of the copper-fullerene composite of the Example, andFIG. 8 shows a mass spectrum of the hydroxyl fullerene of the Synthesis Example. - Comparing these two mass spectra of
FIG. 7 andFIG. 8 , main peaks are overlapped, and the copper-fullerene composite of the Example includes hydroxyl fullerene. - A content of fullerene (C60) and a hydroxyl group (OH) present in the Cu plating layer (including a metal composite material) of the Example depending on current density is examined.
-
FIG. 9 is a graph showing a content of the fullerene (C60) of the Cu plating layer of the Example depending on a current density, andFIG. 10 is a graph showing a content of hydroxyl group (OH) of the Cu plating layer of the Example depending on a current density. - Referring to
FIGS. 9 and 10 , contents of the fullerene (C60) and a hydroxyl group (OH) in the Cu plating layer vary depending on pH and a current density, for example, as the pH is increased, the contents of the fullerene (C60) and the hydroxyl group (OH) are increased in the Cu plating layer, and as the current density is increased, the contents of the fullerene (C60) and the hydroxyl group (OH) are increased in the Cu plating layer. - Accordingly, the contents of the fullerene and the hydroxy group in the Cu plating layer may be adjusted by controlling a condition of the plating.
- A resistivity change of the Cu plating layers according to the Example and the Comparative Example depending on a current density is examined.
- The resistivity change depending on a current density is measured with N5765A made by Agilent Technologies after forming each wire (a length: 30 μm, a width: 10 μm) by using the Cu plating layers of the Example and the Comparative Example as shown in
FIG. 11 . - The results are shown in
FIGS. 12 and 13 . -
FIG. 12 is a graph showing a resistivity change of the Cu plating layers plated at a current density of 0.1 A/m2 of the Example and the Comparative Example, andFIG. 13 is a graph showing a resistivity change of the Cu plating layers plated at a current density of 1.0 A/m2 of the Example and the Comparative Example. - Referring to
FIGS. 12 and 13 , the Cu plating layer of the Example shows a small resistivity change compared with that of the Cu plating layer of the Comparative Example. Accordingly, the Cu plating layer of the Example shows high electrical stability compared with that of the Cu plating layer of the Comparative Example. - Referring to
FIGS. 12 and 13 , ampacity of the Cu plating layers of the Example and the Comparative Example is examined. - The ampacity is defined as a current capacity having resistivity (Dr/r0) of greater than 1 and the resistivity increases as the current increases beyond the ampacity.
- The results are shown in Tables 2 and 3.
-
TABLE 2 Ampacity (milliamperes per square centimeter (mA/cm2)) @ 0.1 A/dm2 Example 17 Comparative Example 6.0 -
TABLE 3 Ampacity (MA/cm2) @ 1.0 A/dm2 Example 26.0 Comparative Example 6.0 - Referring to Tables 2 and 3, the Cu plating layer of the Example shows greater, for example, twice, an ampacity of the Comparative Example.
- While this disclosure has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
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