CN116516427A - Composition for copper plating and method for manufacturing copper-containing conductor using the same - Google Patents
Composition for copper plating and method for manufacturing copper-containing conductor using the same Download PDFInfo
- Publication number
- CN116516427A CN116516427A CN202211131577.7A CN202211131577A CN116516427A CN 116516427 A CN116516427 A CN 116516427A CN 202211131577 A CN202211131577 A CN 202211131577A CN 116516427 A CN116516427 A CN 116516427A
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- CN
- China
- Prior art keywords
- copper
- composition
- copper plating
- plating
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000010949 copper Substances 0.000 title claims abstract description 283
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 282
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 282
- 238000007747 plating Methods 0.000 title claims abstract description 208
- 239000000203 mixture Substances 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000004020 conductor Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 230000008569 process Effects 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 28
- 150000007513 acids Chemical class 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 238000009713 electroplating Methods 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 22
- 150000001879 copper Chemical class 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 230000009467 reduction Effects 0.000 claims description 37
- 239000003112 inhibitor Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229920001451 polypropylene glycol Polymers 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 abstract description 8
- 238000006722 reduction reaction Methods 0.000 description 44
- 229910052751 metal Inorganic materials 0.000 description 33
- 239000002184 metal Substances 0.000 description 33
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 22
- 229910001431 copper ion Inorganic materials 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 230000004888 barrier function Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 5
- -1 salt compound Chemical class 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 208000012868 Overgrowth Diseases 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920000464 Poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- WDSIGTNDHZEPBO-UHFFFAOYSA-N 1-sulfanylethanesulfonic acid Chemical compound SC(C)S(=O)(=O)O.SC(C)S(=O)(=O)O WDSIGTNDHZEPBO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 1
- XXONZJKORUUFIZ-UHFFFAOYSA-N 3-sulfanylpyridine-2-sulfonamide Chemical compound NS(=O)(=O)C1=NC=CC=C1S XXONZJKORUUFIZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- SSOVMNXYUYFJBU-UHFFFAOYSA-L copper;ethanesulfonate Chemical compound [Cu+2].CCS([O-])(=O)=O.CCS([O-])(=O)=O SSOVMNXYUYFJBU-UHFFFAOYSA-L 0.000 description 1
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 1
- BDHAOBSBMMJNGS-UHFFFAOYSA-N copper;propan-1-olate Chemical compound [Cu+2].CCC[O-].CCC[O-] BDHAOBSBMMJNGS-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 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
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000885 poly(2-vinylpyridine) Polymers 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BXEMXLDMNMKWPV-UHFFFAOYSA-N pyridine Chemical group C1=CC=NC=C1.C1=CC=NC=C1 BXEMXLDMNMKWPV-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VYECFMCAAHMRNW-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O.NS(O)(=O)=O VYECFMCAAHMRNW-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920003046 tetrablock copolymer Polymers 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- 229910021341 titanium silicide Inorganic materials 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- 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
-
- 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
Abstract
Embodiments of the present invention provide compositions for copper plating and methods of making copper-containing conductors using the compositions. The composition for copper plating comprises a copper salt, an acidic compound or a salt thereof, a chloride ion source, and a leveling agent represented by the specific chemical formula 1. By the electroplating process using the composition for copper plating, a copper plating film having lower surface roughness, improved surface flatness and thickness uniformity can be formed.
Description
Technical Field
The present invention relates to a composition for copper plating and a method for manufacturing a copper-containing conductor using the same. More particularly, the present invention relates to a composition for copper plating comprising an electrolytic aqueous solution and a leveling agent, and a method for manufacturing a copper-containing conductor using the composition.
Background
In recent years, with the weight, thickness, and size reduction of electronic devices such as smartphones, there is a demand for higher density and higher integration of electronic components such as semiconductor devices, PCBs, flip chips, and the like constituting the electronic devices.
For example, in order to form conductive structures and the like for various electronic components, a via (via) or trench (trench) of a damascene (damascene) process or a through silicon via (through silicon via, TSV) process is filled with a (filling) conductive metal material.
Aluminum (Al), nickel (Ni), tin (Sn), copper (Cu), etc. are used as conductive metal materials for electronic components, and copper has been mainly used recently for acceleration of semiconductor devices. For example, a metal such as copper may be plated at a high speed by an electroplating process to form wirings, electrodes, bumps (bumps) used as connection terminals in flip chips, and the like for semiconductor devices.
However, since the plating rate of the plating process and the current density (current density) applied to the plating solution are proportional to each other, a large current is required to be used in order to plate a metal such as copper at a high speed. Therefore, there may be a region locally on the surface to be plated where the current density is high, and excessive precipitation of metal such as copper may be caused.
Therefore, there is a need for a composition for plating that is capable of uniformly plating a surface to be plated while having a high plating rate. For example, korean patent application publication No. 10-2017-0108848 discloses a copper plating solution and a copper plating method.
Disclosure of Invention
Technical problem
An object of the present invention is to provide a composition for copper plating having excellent plating rate and plating uniformity.
It is an object of the present invention to provide a method for manufacturing copper-containing conductors using the above composition for copper plating.
Technical proposal
1. A composition for copper plating comprising: copper salts; an acidic compound or salt thereof; a source of chloride ions; and a leveling agent including a compound represented by the following chemical formula 1:
[ chemical formula 1]
(in the chemical formula 1, ar is a nitrogen-containing aromatic hydrocarbon group having 4 to 20 carbon atoms, R 1 Is hydrogen, alkyl group having 1 to 7 carbon atoms, alkenyl group having 2 to 7 carbon atoms, alkynyl group having 2 to 7 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, hydroxyl group (-OH), amino group (-NH) 2 ) Carboxyl (-COOH) or amido (-CONH) 2 ) X and y are each independently integers from 1 to 3000).
2. The composition for copper plating as described in 1 above, wherein Ar in the chemical formula 1 contains a pyridine moiety (mole).
3. The composition for copper plating as described in 1 above, wherein the ratio of y to x in the chemical formula 1 is 1 to 3.
4. The composition for copper plating as described in 1 above, wherein the acidic compound comprises sulfuric acid, boric acid, fluoroboric acid, acetic acid, methanesulfonic acid or ethanesulfonic acid.
5. The composition for copper plating as described in 1 above, wherein the salt of the acidic compound comprises at least one of a potassium salt, a sodium salt and an ammonium salt of the acidic compound.
6. The composition for copper plating according to the above 1, wherein in the composition for copper plating, the copper salt is contained in an amount of 10g/L to 300g/L, the acidic compound or salt thereof is contained in an amount of 30g/L to 400g/L, and the chloride ion source is contained in an amount of 5mg/L to 200mg/L.
7. The composition for copper plating as described in the above 1, wherein the leveling agent is contained in the composition for copper plating in an amount of 0.1mg/L to 100mg/L.
8. The composition for copper plating as described in 1 above, further comprising a copper reduction inhibitor or accelerator.
9. The composition for copper plating as described in 8 above, wherein the copper reduction inhibitor comprises polyethylene glycol (PEG), polypropylene glycol (PPG), or a copolymer of polyethylene glycol and polypropylene glycol.
10. The composition for copper plating as described in the above 8, wherein the content of the copper reduction inhibitor in the composition for copper plating is 1mg/L to 5000mg/L.
11. The composition for copper plating according to the above 8, wherein the promoter comprises a sulfur (S) -containing organic compound.
12. The composition for copper plating according to the above 8, wherein the content of the promoter in the composition for copper plating is 0.1mg/L to 300mg/L.
13. A method of making a copper-containing conductor, comprising: forming an insulating layer having an opening over a substrate; and forming a copper film filling the opening by an electroplating process using the composition for copper plating described in 1 above.
14. The method of manufacturing a copper-containing conductor of claim 13 further comprising forming a seed layer covering a surface of the opening prior to the electroplating process.
15. The method of manufacturing a copper-containing conductor as recited in 13 above, wherein the electroplating process is performed at a Current density (Current density) of 1ASD to 30 ASD.
16. The method of manufacturing a copper-containing conductor of claim 13, further comprising: forming an electrode layer on the substrate before forming the insulating layer; and disposing a mask pattern exposing the opening on the insulating layer prior to the electroplating process.
17. The method of manufacturing a copper-containing conductor as in 16 above, wherein a copper bump is provided as the copper-containing conductor, and the method further comprises removing the mask pattern after the electroplating process.
18. The method of fabricating a copper-containing conductor of claim 17 further comprising performing a reflow (reflow) process on the copper bump.
Effects of the invention
The composition for copper plating according to an embodiment of the present invention may include a copper salt, an acidic compound or a salt thereof, a chloride ion source, and a leveling agent represented by the specific chemical formula 1. Therefore, excessive precipitation of copper in the region having a high current density can be prevented, and uniform plating can be performed. Therefore, even at a high plating rate, the copper plating film can be made to have a low surface roughness, and the thickness uniformity and the top surface flatness of the copper plating film can be improved.
In addition, the composition for copper plating may contain a copper reduction inhibitor and/or accelerator. Therefore, the plating rate of the composition for copper plating can be prevented from being too fast or too slow, and copper metal can be uniformly grown on the entire surface to be plated.
In addition, copper-containing conductors can be manufactured using the above-described compositions for copper plating. By the electroplating process using the above composition for copper plating, the generation of cracks (sea) or voids (void) on the surface and inside can be suppressed, and the surface uniformity and packing density of the copper film can be improved.
Drawings
Fig. 1 and 2 are schematic cross-sectional views illustrating a method of manufacturing a copper wiring according to an exemplary embodiment.
Fig. 3 to 5 are schematic cross-sectional views illustrating a method of manufacturing a copper bump according to an exemplary embodiment.
Detailed Description
The composition for copper plating according to an embodiment of the present invention comprises a copper salt, an acidic compound or a salt thereof, a chloride ion source, and a leveling agent.
Further, in the method of manufacturing a copper-containing conductor according to the embodiment of the invention, the copper-containing conductor is formed by using the above-described composition for copper plating. For example, the copper-containing conductors may be used as wires, electrodes, conductors for damascene or TSV, via or trench fills, bumps, and the like.
Hereinafter, embodiments of the present invention will be described in detail.
< composition for copper plating >
The composition for copper plating according to an exemplary embodiment may include a copper salt, an acidic compound or a salt thereof, a chloride ion source, and a leveling agent including a compound having a nitrogen-containing aromatic ring.
Copper salts are provided as a source of copper ions for forming copper plating films. Copper ions dissociated from copper salts may be reduced to copper metal by electrochemical reactions, for example, may be deposited on the surface to be plated to form a copper plating film.
According to an exemplary embodiment, the copper salt may include a water-soluble salt compound, and may dissociate in the aqueous solution to provide copper ions.
For example, the copper salt may include copper sulfate, copper carbonate, copper oxide, copper chloride, copper fluoroborate, copper nitrate, copper phosphate, copper methanesulfonate, copper ethanesulfonate, copper propanolate sulfonate, copper acetate, or copper citrate, and the like. These may be used singly or in combination of two or more.
Preferably, the copper salt may comprise copper sulfate. In this case, the dissociation degree of copper ions in the composition for copper plating can be increased, and plating efficiency can be improved due to the higher copper ion concentration.
In some embodiments, the copper salt may be present in the composition for copper plating in an amount of 10g/L to 300g/L, preferably 50g/L to 200g/L. When the content of copper salt in the composition for copper plating is less than 10g/L, the concentration of copper ions may be low, resulting in a reduction reaction of copper metal, and foreign matter may be contained in the plating film, resulting in a reduction in the purity of the copper plating film and the contact with the substrate. When the copper salt content in the composition for copper plating exceeds 300g/L, copper metal may excessively precipitate, and may cause a decrease in the uniformity, flatness of the plated surface.
The acidic compound or salt thereof may impart conductivity to the composition for copper plating. For example, the acidic compound or salt thereof may be dissociated in a solvent to increase the conductivity of the composition for copper plating. Therefore, the plating rate of copper can be increased in the electroplating process, and a uniform copper plating film can be formed.
In some embodiments, the acidic compound may include an inorganic acid and/or an organic acid.
For example, the inorganic acid may include sulfuric acid, nitric acid, phosphoric acid, boric acid, fluoroboric acid, or the like. These may be used singly or in combination of two or more.
For example, the organic acid may include carboxylic acids such as acetic acid, iminodiacetic acid, ethylenediamine tetraacetic acid, butyric acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, valeric acid, succinic acid, salicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and acrylic acid; and sulfonic acid compounds such as methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, sulfobenzoic acid, sulfosuccinic acid, sulfosalicylic acid, and sulfamic acid (amidosulfonic acid). These may be used singly or in combination of two or more.
For example, salts of acidic compounds may include salts of the above-mentioned inorganic or organic acids. For example, it may comprise a potassium, sodium or ammonium salt of an inorganic acid, or a potassium, sodium or ammonium salt of an organic acid. These may be used singly or in combination of two or more.
In some embodiments, the acidic compound or salt thereof may be present in the composition for copper plating in an amount of 20g/L to 400g/L. When the content of the acidic compound or its salt is less than 20g/L, it may cause a decrease in the conductivity of the composition for copper plating and may cause a decrease in plating efficiency. When the content of the acidic compound or its salt is more than 400g/L, there may be an excessive ion dissociated from the acidic compound or its salt, resulting in an excessive increase in the reactivity of the composition for copper plating and possibly in deterioration of plating quality and uniformity.
Preferably, the content of the acidic compound or a salt thereof in the composition for copper plating may be 30g/L to 150g/L. Within the above range, the composition for copper plating can have a high degree of electrolysis. Therefore, the growth of copper can be promoted even in the region where a low current density flows, thereby improving the surface flatness of the plated film.
In one embodiment, the acidic compound may not include a chloride. For example, the acidic compound may not include a compound that dissociates in the composition to provide chloride ions.
The chloride ion source can increase the copper plating rate in the composition for copper plating or can activate a copper reduction inhibitor to be described later.
For example, when the composition for copper plating does not contain a copper reduction inhibitor, the chloride ion source can enhance the mobility of copper ions in the composition for copper plating and can promote the adsorption of copper ions to enhance the plating rate.
For example, when the composition for copper plating contains a copper reduction inhibitor, the chloride ion source can activate the copper reduction inhibitor, and can adjust the reduction rate and plating rate of copper ions.
In an exemplary embodiment, the chloride ion source may include hydrochloric acid (HCl), sodium chloride (NaCl), potassium chloride (KCl), or ammonium chloride (NH) 4 Cl). These may be used singly or in combination of two or more.
Preferably, the chloride ion source may comprise hydrochloric acid. In this case, the plating rate can be appropriately adjusted, and the copper reduction inhibitor can be made to have high activity because of excellent compatibility with the copper reduction inhibitor.
In some embodiments, the chloride ion source may be present in the composition for copper plating in an amount of 5mg/L to 200mg/L. When the content of the chloride ion source is less than 5mg/L, it may result in a decrease in the activation ability of the copper reduction inhibitor and a decrease in the plating inhibition effect in the region where the high current density is formed. When the content of the chloride ion source exceeds 200mg/L, the content of the chloride ion source may be excessive as compared with the copper reduction inhibitor, so that the balance of the chloride ion source causes an excessive increase in plating rate. Therefore, the surface of the plating film may become rough due to excessive copper reduction reaction.
Preferably, the content of the chloride ion source in the composition for copper plating may be 20mg/L to 150mg/L. In the above range, the copper plating rate can be appropriately adjusted, and the flatness of the plating film can be improved due to excellent compatibility with the copper reduction inhibitor.
The leveling agent can improve the flatness and uniformity of the copper plating film. For example, the leveling agent can be adsorbed in a region where a higher current density is formed in the copper plating process, and by suppressing reduction of copper ions in the region, uniformity and flatness of the copper plating film can be improved.
According to an exemplary embodiment, the leveling agent may include a compound represented by the following chemical formula 1.
[ chemical formula 1]
In chemical formula 1, ar may be a nitrogen-containing aromatic hydrocarbon group having 4 to 20 carbon atoms. For example, ar may be a nitrogen-containing heteroaryl group having 4 to 20 carbon atoms, a nitrogen-containing heteroarylalkyl group having 5 to 20 carbon atoms, or a nitrogen-containing heteroarylalkyl group having 5 to 20 carbon atoms.
R 1 Can be hydrogen, alkyl with 1 to 7 carbon atoms, alkenyl with 2 to 7 carbon atoms, alkynyl with 2 to 7 carbon atoms, cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 10 carbon atoms, hydroxyl (-OH), amino (-NH) 2 ) Carboxyl (-COOH) or amido (-CONH) 2 )。
x and y may each independently be an integer of 1 to 3000.
Each structural unit shown in brackets in chemical formula 1 can be freely positioned at any position in the chain within the specified x and y ranges. Thus, although each bracket in chemical formula 1 is represented as one block in order to present a molar ratio of structural units, each structural unit may be positioned as a block or separated from each other without limitation as long as it is within the compound.
The composition for copper plating according to the exemplary embodiment contains the compound represented by chemical formula 1as a leveling agent, so that the surface roughness of the copper plating film can be improved to suppress the occurrence of cracks (sea) and voids (void), and the top surface flatness can be improved.
For example, when the current density applied to the plating solution is high, metal precipitation in a localized area of the substrate surface may deviate from normal. Therefore, abnormal growth (abnormal growth) defects in which the plated metal film partially overgrows or plating is insufficient may be generated, and an increase in surface roughness may be caused.
In addition, when the surface roughness (roughness) of the copper plating film is high, copper deposition may occur first at the inlet through which the composition flows, not on the surface to be plated, due to unstable copper growth. Therefore, voids may be formed inside the plating film, resulting in a decrease in the packing density of copper, and the internal voids may result in a decrease in electrical connectivity. In addition, localized overgrowth of copper may cause seams (sea) to occur at the surface of the plated film, and may reduce the flatness of the surface and the top surface, resulting in, for example, deterioration of connectivity with external connectors.
Since the compound represented by chemical formula 1 includes a nitrogen-containing aromatic ring, a region of high current density can be formed concentrated on the surface to be plated, and a reduction reaction of copper ions in the region of high current density can be suppressed. Therefore, local abnormal growth due to the difference in current density can be prevented, and a copper plating film having high top surface flatness and uniformity can be provided.
Preferably, in chemical formula 1, ar may include a pyridine (pyridine) moiety (mole).
The leveling agent has a pyridine moiety directly connected with the main chain, so that the leveling agent has stronger adsorptivity to the metal surface in a high current density region. Therefore, the phenomenon that reduction of copper ions is concentrated in the high current density region can be suppressed, and a copper plating film having an overall flat surface can be formed.
In one embodiment, when Ar is a pyridine moiety, the nitrogen atom may be substituted at the ortho (ortho-) position of the benzene ring. In this case, the adsorptivity to the region having a high current density can be further enhanced, and the reduction reaction and excessive precipitation of copper ions in the region can be suppressed.
In addition, R is contained in chemical formula 1 1 The structural unit as a substituent can further improve the adsorption degree of the surface to be plated and suppress the precipitation of copper, so that the copper plating film can have an overall uniform thickness.
In some embodiments, R in formula 1 1 May be an aryl group having 6 to 10 carbon atoms, a hydroxyl group, an amino group, a carboxyl group or an amide group.
In this case, it is possible to pass the substituent R 1 Improving the adsorptivity of the leveling agent to the surface to be plated and improving the inhibition of copper ion reduction reaction in the high current density regionCapability of the application. Therefore, local overgrowth of copper on the surface to be plated can be prevented, and the surface smoothness of the copper plating film can be further improved.
Preferably, R 1 An aryl group having 6 to 10 carbon atoms is possible, and specifically a phenyl group or a benzyl group.
For example, when R in chemical formula 1 1 In the case of phenyl, the leveling agent can be concentrated in a region having a high charge density on the surface to be plated by interaction with an adjacent azaaromatic ring, and can further enhance the inhibition ability against copper reduction reaction. Therefore, the local excessive precipitation and abnormal growth of copper metal can be effectively inhibited, so that the surface roughness of the copper plating film is reduced, and the flatness of the top surface and the thickness uniformity can be further improved.
In some embodiments, the ratio of y to x may be 1 to 3. Within the above range, the plating rate in the high current density region can be appropriately adjusted, and excessive precipitation of copper can be suppressed, so that the copper plating film grows uniformly over the entire surface to be plated.
In some embodiments, the weight average molecular weight (Mw in terms of polystyrene) of the compound represented by chemical formula 1 may be 100 to 500000. The weight average molecular weight may be a value measured by gel permeation chromatography (Gel permeation chromatography, GPC).
In some embodiments, the leveling agent may be present in the composition for copper plating in an amount of 0.1mg/L to 100mg/L. When the content of the leveling agent is less than 0.1mg/L, the cation concentration in the composition for copper plating may be reduced, and the uniformity of the charge density on the surface to be plated may be reduced, thereby reducing the surface roughness and the top surface flatness of the copper plating film.
When the content of the leveling agent exceeds 100mg/L, the cation concentration of the composition for copper plating may be excessively increased, resulting in penetration of cations into the inside of the plating film during the plating process, and the brittleness (britteness) of the plating film may be increased. In addition, the reduction reaction of copper may be suppressed over the entire surface to be plated, resulting in an excessive decrease in plating rate.
Preferably, the leveling agent may be contained in the composition for copper plating in an amount of 1mg/L to 30mg/L. Within the above range, the surface flatness and thickness uniformity of the plated film can be improved without decreasing the plating rate.
According to an exemplary embodiment, the composition for copper plating may further include a copper reduction inhibitor and/or promoter.
The copper reduction inhibitor can play a role in inhibiting copper reduction reaction to adjust copper plating rate. For example, the copper reduction inhibitor can inhibit migration of copper ions in the composition for copper plating, thereby enabling adjustment of the reduction rate of copper. Therefore, by adjusting the copper filling rate at the time of plating, an excessive increase in plating rate can be prevented, and uniformity and flatness of the plated film can be improved.
In some embodiments, the copper reduction inhibitor may include a polyether compound.
For example, the polyether compound may include polyethylene glycol (polyethylene glycol, PEG), polypropylene glycol (polypropylene glycol, PPG), and/or a copolymer of polyethylene glycol (PEG) and polypropylene glycol (PPG). The copolymer of polyethylene glycol and polypropylene glycol may include a diblock copolymer of PEG-PPG, a triblock copolymer of PEG-PPG-PEG, a triblock copolymer of PPG-PEG-PPG, and/or a tetrablock copolymer of PEG-PPG-PEG-PPG. These may be used singly or in combination of two or more.
Preferably, the copper reduction inhibitor may comprise polyethylene glycol. In this case, migration of copper ions can be easily suppressed, and even with a small content, the reduction rate of copper can be easily adjusted.
In some embodiments, the weight average molecular weight (Mw, based on polystyrene) of the copper reduction inhibitor may be from 100 to 100000. The weight average molecular weight may be a value measured by gel permeation chromatography (Gel permeation chromatography, GPC). Within the above range, the reduction rate of copper ions can be appropriately adjusted without degrading plating performance of a structure having a high aspect ratio, such as a via (via) or trench (trench).
In one embodiment, the copper reduction inhibitor may be present in the copper plating composition in an amount of 1 to 5000mg/L. When the content of the copper reduction inhibitor is less than 1mg/L, the concentration of the copper reduction inhibitor in the composition for copper plating may be low, making it difficult to adjust the plating rate. Therefore, the flatness of the plating film may be deteriorated due to an excessive increase in plating rate, resulting in defects in the plating film. When the content of the copper reduction inhibitor exceeds 5000mg/L, the plating rate may be excessively lowered, resulting in a decrease in the efficiency of electroplating.
Preferably, the copper reduction inhibitor may be contained in the composition for copper plating in an amount of 50mg/L to 3000mg/L. The copper plating rate can be appropriately adjusted in the above range, and a composition for copper plating having an improved plating rate and plating uniformity at the time of electroplating can be provided.
An accelerator (accelerator) can increase the plating rate of the composition for copper plating.
In some embodiments, the accelerator may include a sulfur-containing organic compound. For example, the accelerator may include a compound having a sulfonate (sulfonate) type substituent. The sulfur-containing organic compound can increase the reduction rate of copper ions and can increase the plating rate by increasing the copper fill rate during electroplating.
For example, the accelerator may include bis- (3-sulfopropyl) disulfide (SPS), mercaptoethane sulfonic acid (mercaptoethane sulfonic acid), 3-mercapto-1-propane sulfonic acid (3-mercapto-1-propanesulfonic acid, MPSA), or 3-N, N-dimethylaminodithiocarbamoyl-1-propane sulfonic acid (3-N, N-dimethylthiocarbamoyl-1-propanesulfonic acid, DPS), and the like. These may be used singly or in combination of two or more.
Preferably, the accelerator may comprise bis- (3-thiopropyl) disulphide.
In one embodiment, the accelerator may be present in the composition for copper plating in an amount of 0.1mg/L to 300mg/L. When the content of the accelerator is less than 0.1mg/L, the concentration of the accelerator may be low, resulting in a decrease in the plating rate. When the content of the accelerator exceeds 300mg/L, the copper plating rate may be excessively increased due to excessive reduction reaction, and the flatness of the copper plating film may be deteriorated.
Preferably, the accelerator may be contained in the composition for copper plating in an amount of 1mg/L to 30mg/L. In the above range, the reduction reaction and plating rate of copper ions can be appropriately adjusted, and the surface flatness of the plated film can be improved.
In some embodiments, the composition for copper plating may include a solvent to dissolve the above components. In one embodiment, the composition for copper plating may contain water as a solvent. For example, the composition for copper plating may contain deionized water (DIW), and the resistivity of the deionized water may be 18mΩ/cm or higher.
< method for producing copper-containing conductor >
The method of manufacturing a copper-containing conductor according to an embodiment of the present invention may be performed by an electroplating process using the above-described composition for copper plating.
For example, fig. 1 and 2 describe a method of manufacturing copper wiring, and fig. 3 to 5 describe a method of manufacturing copper bumps.
However, the above-described composition for copper plating is not limited to the manufacturing process shown in fig. 1 to 5, but may be applied to various manufacturing processes for forming copper conductors, such as a dual damascene (dual damascene) process or a through silicon via (through silicon via, TSV) process. For example, the above composition for copper plating can be applied to various processes to fill a via (via hole) or trench (trench) with a copper-containing conductive material.
Hereinafter, a method for manufacturing a copper-containing conductor using the above composition for copper plating will be described in detail with reference to the accompanying drawings.
Fig. 1 and 2 are schematic cross-sectional views for explaining a method of manufacturing a copper wiring according to an exemplary embodiment.
Referring to fig. 1, an insulating layer 20 may be formed on a substrate 10, and the insulating layer 20 may include an opening 22.
The substrate 10 may include a single crystal Silicon substrate, a polycrystalline Silicon substrate, a Silicon germanium substrate, a Silicon-On-Insulator (SOI) substrate, a germanium-On-Insulator (GOI) substrate, a metal oxide single crystal substrate, and the like.
The insulating layer 20 may include an insulating material such as oxide, nitride, or oxynitride. For example, the insulating layer 20 may include silicon oxide, silicon nitride, silicon oxynitride, or the like.
In some embodiments, a metal base film 30 may be formed covering the surface of the opening 22. For example, the metal base film 30 may be formed to cover the side walls and the bottom surface of the opening 22. For example, the metal base film 30 may include a seed layer.
The seed layer may act as a base layer for copper metal to grow in the openings 22 and may improve the reduction rate of copper ions. For example, the seed layer may contain copper, and may also contain gold (Au), silver (Ag), platinum (Pt), or ruthenium (Ru). The seed layer may be formed by Chemical Vapor Deposition (CVD), physical Vapor Deposition (PVD), atomic Layer Deposition (ALD), or the like.
In one embodiment, the metal base film 30 may further include a diffusion barrier layer. In this case, the metal base film 30 may be formed on the insulating layer 20 and may include a diffusion barrier layer covering the hole and a seed layer covering the diffusion barrier layer.
The diffusion barrier layer may function as a barrier (barrier) layer that prevents copper metal from diffusing into the insulating layer 20 and the substrate 10. For example, the diffusion barrier layer may include titanium (Ti), tantalum (Ta), chromium (Cr), tungsten (W), oxides/nitrides thereof, or alloys thereof. For example, the diffusion barrier layer may include titanium, titanium nitride, titanium silicide nitride, tantalum nitride, tantalum silicide nitride, tungsten nitride, and the like.
Referring to fig. 2, a copper film 40 may be formed on the insulating layer 20 or the metal base film 30 to fill the opening 22. The opening 22 may be filled with the copper film 40 by an electroplating method using the composition for copper plating described above.
In one embodiment, the copper film 40 may be formed by loading (loadimg) the substrate 10 formed with the insulating layer 20 into a copper plating apparatus and impregnating with the above-described composition for copper plating. In this case, a current may be supplied to the surface of the metal base film 30 so as to have a current density (current density) of 1ASD to 30ASD (Ampere per Square Decimetre amperes per square decimeter).
Preferably, the current density applied to the surface of the metal base film 30 may be 10ASD to 20ASD. In this case, the amount of copper deposited per unit time can be increased, and the plating rate can be increased. Further, by electroplating using the composition for copper plating described above, the thickness uniformity of the copper film can be improved, and a copper film excellent in the flatness of the top surface can be formed.
In some embodiments, the copper film 40 may be removed to expose an upper surface of the insulating layer 20. Subsequently, copper wiring filling the opening 22 may be formed. In one embodiment, the copper film 40 covering the upper surface of the insulating layer 20 may be removed by a planarization process such as a chemical mechanical polishing (Chemical Mechanical Polishing, CMP) process.
In one embodiment, the copper film 40 is removed, and the metal base film 30 covering the upper surface of the insulating layer 20 is also removed.
By forming copper wiring using the above composition for copper plating, plating uniformity can be improved, and the upper surface of the copper wiring can be made to have excellent flatness. Therefore, it is possible to make the copper wiring have a fine size and high uniformity, and for example, a semiconductor device having high integration and high density can be manufactured.
Fig. 3 to 5 are schematic cross-sectional views for describing a method of manufacturing a copper bump according to an exemplary embodiment.
Referring to fig. 3, an electrode layer 120 may be formed on a substrate 100, and an insulating layer may be formed on the substrate 100 to expose at least a portion of the electrode layer 120. For example, the insulating layer may have a hole exposing at least a portion of the upper surface of the electrode layer 120.
The substrate 100 may include a single crystal silicon substrate, a polycrystalline silicon substrate, a silicon germanium substrate, an SOI substrate, a GOI substrate, a metal oxide single crystal substrate, and the like.
The electrode layer 120 may be a conductive structure such as a wiring, a pad, a connection element, a gate electrode, a capacitor electrode, a contact, and a plug.
The insulating layer may have a stacked structure of the first insulating layer 110 and the second insulating layer 130. For example, the first insulating layer 110 may be formed on the substrate 100 to expose at least a portion of the electrode layer 120, and the second insulating layer 130 may be formed on the first insulating layer 110.
The first insulating layer 110 may function as a buffer layer for relieving stress that may occur in a manufacturing process of the copper bump 162, such as a copper plating process and a reflow (reflow) process.
For example, the first insulating layer 110 may include an organic polymer material such as polyimide, or an insulating material such as silicon oxide or silicon nitride. Preferably, it may comprise an organic polymeric material having relatively high stress relief properties.
The second insulating layer 130 may include an insulating material such as oxide, nitride, and/or oxynitride, or a low dielectric material. For example, the second insulating layer 130 may include silicon oxide, silicon nitride, or the like.
In some embodiments, a metal base film 140 covering the hole surface may be formed. For example, the metal base film 140 may be formed to cover the sidewall and bottom surface of the hole. The metal base film 140 may function as a base layer disposed between the electrode layer 120 and the copper plating film.
In some embodiments, the metal base film 140 may include a diffusion barrier layer and a seed layer disposed sequentially from the substrate 100.
The diffusion barrier layer may function as a barrier layer that prevents copper from diffusing into the electrode layer 120 and the insulating layer during a copper plating process or a reflow process. For example, the diffusion barrier layer may comprise titanium (Ti), tantalum (Ta), chromium (Cr), tungsten (W), oxides/nitrides thereof, or alloys thereof.
The seed layer may act as a base layer for the copper plating to grow. For example, a copper film may be grown from the surface of the seed layer by an electroplating process to fill holes disposed between insulating layers or openings 152 formed between mask patterns 150. In an embodiment, the seed layer may include copper, and may further include gold (Au), silver (Ag), platinum (Pt), or ruthenium (Ru).
In one embodiment, the seed layer may be formed by Chemical Vapor Deposition (CVD), physical Vapor Deposition (PVD), atomic Layer Deposition (ALD), or the like.
A mask pattern 150 may be formed on the second insulating layer 130 and/or the metal base film 140. The mask pattern 150 may be formed to have an opening 152 exposing the hole. For example, the plurality of mask patterns 150 may be arranged to be spaced apart to expose the holes.
The mask pattern 150 may include a material having an etching selectivity with respect to the second insulating layer 130. For example, the mask pattern 150 may be a photoresist pattern or a hard mask.
Referring to fig. 4, a copper film 160 filling the opening 152 may be formed on the insulating layer and/or the metal base film 40. For example, the copper film 160 may be formed by electroplating using the composition for copper plating described above.
In an embodiment, the copper film 160 may be formed by loading the substrate 100 formed with the mask pattern 150 into a copper plating apparatus and impregnating with the above-described composition for copper plating. In this case, a current may be supplied to the surface of the metal base film 140 to have a current density of 1ASD to 30 ASD. Preferably, the current density applied to the surface of the metal base film 140 may be 10ASD to 20ASD.
By performing the electroplating process using the above composition for copper plating, the thickness uniformity of the copper film can be improved even at a higher plating rate, and a copper film having excellent top surface flatness can be formed.
Referring to fig. 5, after removing the mask pattern 150, a reflow (reflow) process may be performed on the copper plating film. Accordingly, the copper plating film may be formed as spherical copper bumps 162 in electrical contact with the electrode layer 120 disposed on the substrate 100.
In an embodiment, the metal base film 140 may be removed from the second insulating layer 130 using the copper film 160 as an etching mask. For example, the metal base film 140 may be etched to expose the upper surface of the second insulating layer 130 in the region where the copper film 160 is not formed. In this case, the metal base film 140 may function as a relay layer disposed between the electrode layer 120 and the copper bump 162.
By forming copper bumps using the composition for copper plating described above, the top surface flatness and uniformity of the copper bumps can be further improved. Accordingly, the copper bump can have a low surface roughness and inclination, so that a sufficient contact area can be ensured for the external connection.
Hereinafter, experimental examples including preferred examples and comparative examples are provided to aid in understanding the present invention, but these examples are merely to illustrate the present invention and do not limit the appended claims. It will be apparent to those skilled in the art that various changes and modifications can be made to the embodiments within the scope and technical spirit of the invention and that such changes and modifications naturally fall within the scope of the appended claims.
Examples and comparative examples: preparation of composition for copper plating
Example 1
Copper sulfate pentahydrate (CuSO) 4 ·5H 2 O) preparation of a solution containing copper ions and sulfuric acid (H) 2 SO 4 ) And aqueous copper salt electrolyte solutions of hydrochloric acid (HCl). Bis (3-thiopropyl) disulfide (SPS) was added as an accelerator and polyethylene glycol (Mw: 4000) was added as an inhibitor to the copper salt electrolyte aqueous solution, followed by stirring. After that, the compound (a-1) represented by chemical formula 1 was added as a leveling agent.
Specifically, ar of A-1 is a pyridine moiety, R 1 Is any one of aryl, hydroxyl, amino, carboxyl and amido with 6 to 10 carbon atoms.
In A-1, x and y are integers of 1 or more, and the sum of x and y is 3000.
The components were added to satisfy the contents shown in table 1 below.
Examples 2 to 8 and comparative examples
Compositions for copper plating according to examples and comparative examples, which were prepared by mixing the components shown in the following table 1 at the same content as in example 1, were prepared.
TABLE 1
The specific component names listed in table 1 are as follows.
Copper salt (A)
Copper sulfate (CuSO) 4 ·5H 2 O)
Acidic Compound (B)
Sulfuric acid (H) 2 SO 4 )
Chloride ion source (C)
Hydrochloric acid (HCl)
Leveling agent (D)
A-2: poly (2-vinylpyridine) represented by the following chemical formula 2 (Mw: 16000)
[ chemical formula 2]
A-3: imidazole (imidozole)
Promoter (E)
Bis- (3-thiopropyl) disulfide (SPS)
Inhibitors (F)
Polyethylene glycol (Mw: 4000)
Experimental example
Copper plating film production
Copper plating films were produced by an electroplating method using the compositions for copper plating prepared in examples and comparative examples, respectively, as plating solutions.
Specifically, a silicon wafer having a pattern formed thereon is prepared. A plating solution containing a composition for copper plating is placed in a plating tank of a plating apparatus, and a silicon wafer is immersed in the plating solution. Thereafter, a current is applied to perform copper plating. At this time, a current was applied at a current density of 20ASD, and copper plating was performed so that the thickness of the copper plating film was 40. Mu.m.
Thereby, a copper plating film between the filling patterns is formed on the silicon wafer.
Evaluation of flatness of copper coating film
The profile of the copper plating film scanned using the surface analyzer was confirmed for the manufactured copper plating film. The copper plating film is formed such that the middle portion of the upper portion of the pattern is convex or concave, and the flatness of the plating film is evaluated by measuring the difference between the height of the highest point of the upper surface of the pattern and the height of the lowest point of the upper surface of the pattern. .
The evaluation criteria are as follows.
< evaluation criteria >
The height difference is less than 2 mu m
O: the height difference is above 2 μm and below 4 μm
Delta: the height difference is above 4 μm and less than 5 μm
X: the height difference is above 5 μm
TABLE 2
Referring to tables 1 and 2, it can be confirmed that when electroplating was performed using the composition for copper plating according to the exemplary embodiment, the surface flatness of the plated film was very excellent even if the current density was increased to 20ASD.
Therefore, when the composition for copper plating according to the embodiment is used, a copper film having excellent surface flatness can be formed while maintaining a high plating rate.
However, in the case of plating using the composition for copper plating according to the comparative example, it was confirmed that the film thickness uniformity of the plating film was deteriorated due to the high current density.
It was confirmed that in the case of comparative example 1 lacking a leveling agent and comparative examples 4 and 5 containing imidazole as a leveling agent, the surface flatness was significantly deteriorated as compared with examples.
As for comparative examples 2 and 3, the leveling agent lacks the substituent group R according to the examples 1 It can be confirmed that the surface unevenness is higher than the composition for copper plating according to the example. Therefore, it was confirmed that R was contained due to the lack of the substituent 1 Because of the structural unit of (2)This results in a reduction inhibition capability of copper ions in the high current density region being reduced, so that excessive deposition of copper occurs.
Claims (18)
1. A composition for copper plating comprising:
copper salts;
an acidic compound or salt thereof;
a source of chloride ions; and
a leveling agent comprising a compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, ar is a nitrogen-containing aromatic hydrocarbon group having 4 to 20 carbon atoms,
R 1 is hydrogen, alkyl group having 1 to 7 carbon atoms, alkenyl group having 2 to 7 carbon atoms, alkynyl group having 2 to 7 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, hydroxyl group (-OH), amino group (-NH) 2 ) Carboxyl (-COOH) or amido (-CONH) 2 )，
x and y are each independently integers from 1 to 3000.
2. The composition for copper plating according to claim 1, wherein Ar in the chemical formula 1 contains a pyridine moiety.
3. The composition for copper plating according to claim 1, wherein the ratio of y to x in the chemical formula 1 is 1 to 3.
4. The composition for copper plating according to claim 1, wherein the acidic compound comprises sulfuric acid, boric acid, fluoroboric acid, acetic acid, methanesulfonic acid, or ethanesulfonic acid.
5. The composition for copper plating according to claim 1, wherein the salt of the acidic compound comprises at least one of a potassium salt, a sodium salt, and an ammonium salt of the acidic compound.
6. The composition for copper plating according to claim 1, wherein in the composition for copper plating,
the copper salt content is 10g/L to 300g/L,
the content of the acidic compound or the salt thereof is 30g/L to 400g/L,
the content of the chloride ion source is 5mg/L to 200mg/L.
7. The composition for copper plating according to claim 1, wherein the leveling agent is contained in the composition for copper plating in an amount of 0.1mg/L to 100mg/L.
8. The composition for copper plating according to claim 1, further comprising a copper reduction inhibitor or accelerator.
9. The composition for copper plating according to claim 8, wherein the copper reduction inhibitor comprises polyethylene glycol (PEG), polypropylene glycol (PPG), or a copolymer of polyethylene glycol and polypropylene glycol.
10. The composition for copper plating according to claim 8, wherein the copper reduction inhibitor is contained in the composition for copper plating in an amount of 1mg/L to 5000mg/L.
11. The composition for copper plating according to claim 8, wherein the accelerator comprises a sulfur (S) -containing organic compound.
12. The composition for copper plating according to claim 8, wherein the accelerator is contained in the composition for copper plating in an amount of 0.1mg/L to 300mg/L.
13. A method of making a copper-containing conductor, comprising:
forming an insulating layer having an opening over a substrate; and
a copper film filling the opening is formed by an electroplating process using the composition for copper plating according to claim 1.
14. The method of fabricating a copper-containing conductor of claim 13 further comprising forming a seed layer covering a surface of the opening prior to the electroplating process.
15. The method of fabricating a copper-containing conductor of claim 13 wherein the electroplating process is performed at a current density of 1ASD to 30 ASD.
16. The method of making a copper-containing conductor of claim 13 further comprising:
forming an electrode layer on the substrate before forming the insulating layer; and
a mask pattern exposing the opening is disposed on the insulating layer prior to the electroplating process.
17. The method of manufacturing a copper-containing conductor of claim 16 wherein a copper bump is provided as the copper-containing conductor, and further comprising removing the mask pattern after the electroplating process.
18. The method of fabricating a copper-containing conductor of claim 17 further comprising performing a reflow process on the copper bump.
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| KR1020220009049A KR20230112884A (en) | 2022-01-21 | 2022-01-21 | Composition for plating copper and method of forming conductors including copper using the same |
| KR10-2022-0009049 | 2022-01-21 |
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| CN116516427A true CN116516427A (en) | 2023-08-01 |
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| KR (1) | KR20230112884A (en) |
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