CN105593405A - 在阻障层上沉积铜晶种层的方法和铜电镀浴 - Google Patents
在阻障层上沉积铜晶种层的方法和铜电镀浴 Download PDFInfo
- Publication number
- CN105593405A CN105593405A CN201480052336.0A CN201480052336A CN105593405A CN 105593405 A CN105593405 A CN 105593405A CN 201480052336 A CN201480052336 A CN 201480052336A CN 105593405 A CN105593405 A CN 105593405A
- Authority
- CN
- China
- Prior art keywords
- barrier layer
- seed layer
- crystal seed
- copper
- ion
- 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.)
- Granted
Links
- 239000010949 copper Substances 0.000 title claims abstract description 173
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 154
- 230000004888 barrier function Effects 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000007747 plating Methods 0.000 title abstract description 14
- 238000000151 deposition Methods 0.000 title description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 43
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims abstract description 32
- -1 Cu(II) ions Chemical class 0.000 claims abstract description 24
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims description 89
- 238000009713 electroplating Methods 0.000 claims description 61
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 54
- 238000007772 electroless plating Methods 0.000 claims description 45
- 239000000080 wetting agent Substances 0.000 claims description 41
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 35
- 229910052707 ruthenium Inorganic materials 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000085 borane Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003989 dielectric material Substances 0.000 claims description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 5
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 150000004780 naphthols Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 claims 1
- 229910000104 sodium hydride Inorganic materials 0.000 claims 1
- 239000012312 sodium hydride Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 29
- 238000003287 bathing Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000004626 scanning electron microscopy Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
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- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000005837 radical ions Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 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
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-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
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- JJFNJZGXHWYGMQ-UHFFFAOYSA-N [Ni].B#[Co] Chemical compound [Ni].B#[Co] JJFNJZGXHWYGMQ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004020 conductor Substances 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
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-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
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PANJMBIFGCKWBY-UHFFFAOYSA-N iron tricyanide Chemical compound N#C[Fe](C#N)C#N PANJMBIFGCKWBY-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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Abstract
本发明涉及一种在阻障层的顶部提供铜晶种层的方法,其中所述晶种层从水性无电铜电镀浴沉积于所述阻障层上,所述无电铜电镀浴包含Cu(II)离子的水溶性来源、Cu(II)离子的还原剂、Cu(II)离子的至少一种络合剂以及选自由RbOH、CsOH和其混合物组成的群组的至少一种氢氧根离子来源。所得铜晶种层具有均匀厚度分布和光滑外表面,这都是需要的特性。
Description
技术领域
本发明涉及一种在充当连续电镀的电镀基底的阻障层上沉积铜晶种层的方法。根据本发明的方法尤其适用于微芯片等的制造中的双镶嵌电镀。
背景技术
金属的电镀,尤其铜电镀在由例如钌和钴的典型阻障材料制成的衬底表面的情况下,需要导电晶种层。此类晶种层原则上可由任何种类的导电材料组成。然而,由于铜的固有电导率较高,因此铜晶种层是优选的。
所述晶种层必须满足若干要求,例如对底层阻障层和通过电镀沉积于所述晶种层顶部的金属的足够粘附力。此外,晶种层应具有均匀(狭窄)厚度分布和光滑外表面。此类要求在微芯片等的制造中尤其重要,其中需要涂布有此类铜晶种层的嵌入型结构的尺寸可低至纳米范围内。
在由钌制成的阻障层上电镀铜晶种层的方法揭露于US7,998,859B2和US7,470,617B2中。两种方法都利用包含还原剂的水溶液在无电铜电镀之前从钌阻障层去除非所需表面氧化物。两种方法进一步利用标准无电铜电镀浴组合物,其包含NaOH或KOH作为氢氧根离子的唯一来源。铜晶种层的外表面的粗糙度在两种情况下都过高(比较实例1到比较实例4)。
因此,需要提供通过无电电镀沉积于阻障层上的薄铜层,其产生外表面具有改良光滑度的铜晶种层。
发明内容
本发明的目标
本发明的目标为提供一种在阻障层上沉积铜晶种层以供连续电镀的方法,所述阻障层具有均匀厚度分布和光滑外表面。
本发明的概述
通过一种在阻障层的顶部提供铜晶种层的方法解决此目标,所述方法依序包含以下步骤:
(i)提供至少在外表面的一部分上包含阻障层的衬底,
(ii)使所述衬底与水性无电铜电镀浴接触,所述无电铜电镀浴包含
a.Cu(II)离子的水溶性来源,
b.Cu(II)离子的还原剂,
c.Cu(II)离子的至少一种络合剂和
d.选自由RbOH、CsOH和其混合物组成的群组的至少一种氢氧根离子来源。
通过根据本发明的方法获得的阻障层顶部的铜晶种层提供对底层阻障层和电镀于所述铜晶种层上的金属层的足够粘附力。此外,铜晶种层具有均匀厚度分布和所需光滑表面。在通过无电电镀将铜晶种层沉积于阻障层上之前,不需用贵金属活化剂活化所述阻障层。
附图说明
图1展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描电子显微相片,所述无电电镀浴含有NaOH作为氢氧根离子的唯一来源和乙醛酸作为还原剂(实例1(比较实例))。
图2展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描原子力显微(AFM)相片,所述无电电镀浴含有NaOH作为氢氧根离子的唯一来源和乙醛酸作为还原剂(实例1(比较实例))。
图3展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描电子显微相片,所述无电电镀浴含有NaOH作为氢氧根离子的唯一来源和甲醛作为还原剂(实例2(比较实例))。
图4展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描原子力显微(AFM)相片,所述无电电镀浴含有NaOH作为氢氧根离子的唯一来源和甲醛作为还原剂(实例2(比较实例))。
图5展示在钴阻障层上从无电电镀浴获得的铜晶种层的扫描电子显微相片,所述无电电镀浴含有NaOH作为氢氧根离子的唯一来源和乙醛酸作为还原剂(实例3(比较实例))。
图6展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描电子显微相片,所述无电电镀浴含有KOH作为氢氧根离子的唯一来源和甲醛作为还原剂(实例4(比较实例))。
图7展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描原子力显微(AFM)相片,所述无电电镀浴含有KOH作为氢氧根离子的唯一来源和甲醛作为还原剂(实例4(比较实例))。
图8展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描电子显微相片,所述无电电镀浴含有CsOH作为氢氧根离子的唯一来源和乙醛酸作为还原剂(实例5(本发明))。
图9展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描原子力显微(AFM)相片,所述无电电镀浴含有CsOH作为氢氧根离子的唯一来源和乙醛酸作为还原剂(实例5(本发明))。
图10展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描电子显微相片,所述无电电镀浴含有CsOH作为氢氧根离子的唯一来源和甲醛作为还原剂(实例6(本发明))。
图11展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描原子力显微(AFM)相片,所述无电电镀浴含有CsOH作为氢氧根离子的唯一来源和甲醛作为还原剂(实例6(本发明))。
图12展示在钴阻障层上从无电电镀浴获得的铜晶种层的扫描电子显微相片,所述无电电镀浴含有CsOH作为氢氧根离子的唯一来源和乙醛酸作为还原剂(实例7(本发明))。
图13展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描原子力显微(AFM)相片,所述无电电镀浴含有氢氧化四甲铵作为氢氧根离子的唯一来源和乙醛酸作为还原剂(实例8(比较实例))。
图14展示在钌阻障层上从无电电镀浴获得的铜晶种层的扫描原子力显微(AFM)相片,所述无电电镀浴含有氢氧化四丁基铵作为氢氧根离子的唯一来源和乙醛酸作为还原剂(实例9(比较实例))。
具体实施方式
适用于在根据本发明的阻障层的顶部提供铜晶种层的方法的衬底材料优选选自硅、硅衬底上的低κ介电材料和玻璃。由此类材料制成的电子装置包含微芯片、玻璃插入件等。此类衬底材料中的嵌入型结构需要涂布或填充有通常通过电镀沉积的金属。最相关的金属为经电镀的铜。
在根据本发明的阻障层的顶部提供铜晶种层的方法的一个具体应用是将金属电镀到极其精细的嵌入型结构中,所述嵌入型结构被蚀刻到硅衬底、硅衬底上的低κ介电材料中。典型的低κ介电材料在所属领域中已知且包含氟掺杂的二氧化硅、碳掺杂的二氧化硅、多孔二氧化硅、多孔碳掺杂的二氧化硅、聚酰亚胺、聚降冰片烯、苯并环丁烷、PTFE以及旋涂式基于聚硅氧的聚合介电质,例如氢-倍半氧硅烷和甲基-倍半氧硅烷。
此类极精细的嵌入型结构可为盲孔(仅具有一个开口)、穿孔(在两侧都具有开口)以及沟槽(线型图案等)。此类嵌入型结构通常具有例如14nm到几百微米或甚至毫米范围内的几何尺寸。
此具体应用可分为
1.双镶嵌应用,其中嵌入型结构形成于硅和/或低κ介电材料中且具有在纳米或较低微米范围内的开口尺寸。铜晶种层可具有1nm至20nm范围内的厚度和
2.硅穿孔(TSV)的填充物,其为在硅和/或硅衬底上的低κ介电材料中的盲孔。TSV的开口在微米范围内且铜晶种层可具有高达几百纳米或甚至1微米或1微米以上的厚度。
于阻障层的顶部的铜晶种层的另一具体应用在显示器的制造中,例如基于液晶的显示器,其中玻璃衬底涂布有一或多个金属阻障层。可通过在一或多个阻障层上沉积具有光滑外表面的铜晶种层,继而在上面电镀例如铜的金属来形成电路。
所有这些应用都需要铜晶种层的均匀厚度分布和光滑外表面。
在许多情况下,必须抑制所述经电镀金属进入衬底材料中或衬底材料进入经电镀金属中的非所需扩散和相关过程以便获得和/或维持最终电子装置的所需特性。因此,借助于一或多个阻障层分隔经电镀金属,所述阻障层通过以下方法沉积:例如化学气相沉积(CVD)、物理气相沉积(PVD)和原子层沉积(ALD)的气相方法和前述的等离子增强型方法或例如无电电镀的湿式化学工艺。在两个或两个以上个别阻障层材料的堆叠的情况下,仅最外部阻障层将与无电铜电镀浴接触。在两个或两个以上个别阻障层的堆叠的情况下,单种阻障层材料或最外部阻障层材料选自钴、镍、钌、钨、钼、钽、钛、铱、铑和前述的合金。
所述“前述的合金”包含例如氮化钨、氮化钽和氮化钴(例如Co4N)的氮化物以及磷化物和硼化物,例如钴-和镍-磷或-硼合金、三元钴-和镍-磷合金和三元钴-和镍-硼合金(例如,Ni-Mo-P、Ni-W-P、Co-Mo-P、Co-W-P、Co-W-B)。
所述阻障层或最外部阻障层的厚度在若干阻障层的堆叠的情况下通常具有1nm至20nm范围内的厚度。
从阻障层去除非所需表面氧化物:
如果在个别阻障层的堆叠的情况下单种阻障层材料或最外部阻障层材料为钌层,那么可能需要在通过无电电镀沉积铜晶种层之前去除存在于所述阻障层材料的外表面顶部的表面氧化物,因为其可能阻止铜晶种层完全覆盖在所述阻障层的整个外表面上。
可通过使用例如N2/H2等离子处理钌表面和/或通过使用在溶剂中提供的还原剂处理钌表面,在步骤(ii)之前充分地去除所述表面氧化物。
从阻障层湿式-化学去除非所需表面氧化物:
用于充分去除所述表面氧化物的溶剂中的适合还原剂选自包含乙醛酸、甲醛、次磷酸盐、肼、二甲氨基硼烷、三甲氨硼烷、N-甲基吗啉基硼烷和硼氢化钠的群组。所述还原剂在溶剂中的浓度优选在0.001mol/l到10mol/l,更优选0.005mol/l到5mol/l且最优选0.01mol/l到2mol/l范围内。
溶剂优选选自包含水、例如异丙醇的醇类、例如二乙二醇的二醇醚和其混合物的群组。水与前述有机溶剂中的一或多者的混合物优选包含50重量%的水且更优选低于50重量%的水。当利用所述水-(有机)溶剂代替纯水或含有超过50重量%水的水-(有机)溶剂混合物时,还原剂的稳定性提高。
具有钌阻障层的衬底优选与溶剂中的所述还原剂接触30秒到20分钟且更优选1分钟到10分钟。在所述工艺步骤期间还原剂-溶剂混合物的温度优选保持在20℃到90℃且更优选50℃到90℃范围内。
所述还原剂-溶剂混合物优选包含湿润剂,例如阳离子湿润剂、阴离子湿润剂、非离子湿润剂、两性湿润剂以及其混合物。此种类型的湿润剂例如揭露于US7,998,859B2中。
湿润剂在还原剂-溶剂混合物中的浓度优选在0.1g/l到100g/l,更优选0.25g/l到25g/l且最优选0.5g/l到15g/l范围内。
用于充分去除钌阻障层的外表面上的非所需表面氧化物的另一种适合湿式-化学方法为用初生氢处理钌阻障层,所述初生氢通过在溶剂中将阴极电流施加到与所述溶剂接触的衬底原位生成。在这一实施例中,初生氢充当溶剂中所提供的还原剂。
施加到衬底的电压优选在0.5V到20V,更优选1V到15V且最优选2V到10V范围内,且将其保持1秒到360秒,更优选10秒到180秒且最优选20秒到120秒。溶剂优选选自包含水、例如异丙醇的醇类、例如二乙二醇的二醇醚和其混合物的群组。
在这一工艺步骤期间将含有原位形成的初生氢的溶剂保持在10℃到80℃,更优选15℃到60℃且最优选20℃到40℃范围内的温度下。
溶剂优选包含选自阳离子湿润剂、阴离子湿润剂、非离子湿润剂、两性湿润剂和其混合物的湿润剂。溶剂更优选包含非离子湿润剂或两种或两种以上非离子湿润剂的混合物。溶剂最优选包含选自包含聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物、例如分支链仲醇乙氧基化物和乙氧基化苯酚或萘酚的醇烷氧基化物、例如乙氧基化脂肪酸的烷氧基化脂肪酸和其混合物的群组的非离子湿润剂。所述非离子湿润剂尤其支持用初生氢作为还原剂的表面氧化物的所需去除。
湿润剂在溶剂中的浓度或所有湿润剂一起(在利用超过一种湿润剂的情形中)的浓度优选在0.5g/l到100g/l,更优选1g/l到25g/l且最优选5g/l到15g/l范围内。
在本发明的一个实施例中,组合所述用于还原钌阻障层顶部的表面氧化物的方式中的两者或两者以上。使用例如水的冲洗液体的冲洗步骤可在步骤(ii)之前分离所述用于还原表面氧化物的所述手段。冲洗液体可进一步包含优选选自包含聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物、例如分支链仲醇乙氧基化物和乙氧基化苯酚或萘酚的醇烷氧基化物、例如乙氧基化脂肪酸的烷氧基化脂肪酸和其混合物的群组的非离子湿润剂。
任选的非离子湿润剂在冲洗液体中的浓度或所有湿润剂一起(在利用超过一种非离子湿润剂的情形中)的浓度优选在0.5g/l到100g/l,更优选1g/l到25g/l且最优选5g/l到15g/l范围内。
在根据本发明的方法的步骤(ii)之前,衬底可例如用水冲洗。
不适于通过无电(自催化)电镀在上面沉积铜层的阻障层材料在根据本发明的方法的步骤(ii)之前需要各别活化。所述活化在所属领域中已知且例如用于制造印刷电路板等。因此,不适于通过无电式(自催化)电镀在上面沉积铜层的阻障层材料可例如通过浸没电镀将例如钯的贵金属沉积于所述阻障层材料上来活化,所述阻障层材料随后适于通过无电(自催化)电镀在上面沉积铜。
在阻障层上的铜晶种层的无电电镀:
此类阻障层的一个特定缺点为其电导率通常比例如铜的电导率低得多。因此,连续电镀需要与阻障层材料相比具有提高的电导率的铜晶种层。
所述铜晶种层的厚度针对例如硅穿孔的填充物和显示器的制造优选在50nm到2μm范围内。在双镶嵌应用的情况下,铜晶种层的厚度优选在1nm到20nm范围内。
在根据本发明的方法的步骤(ii)中,通过无电电镀将铜晶种层沉积在阻障层(或在两种或两种以上个别阻障层的堆叠的情况下最外部阻障层)上。
“无电电镀”意思是“自催化电镀”。因此,在步骤(ii)中利用的铜电镀浴包含针对Cu(II)离子的还原剂。
在根据本发明的方法中利用的无电铜电镀浴优选为水性电镀浴,也就是说溶剂为水。
Cu(II)离子的水溶性来源优选选自包含硫酸铜、氯化铜、硝酸铜、乙酸铜、甲烷磺酸铜、氢氧化铜、甲酸铜和其水合物的群组。无电电镀浴中的Cu(II)离子的浓度优选在0.05g/l到20g/l,更优选0.1g/l到10g/l且最优选0.2g/l到6g/l范围内。
无电电镀浴进一步含有选自包含甲醛、乙醛酸、葡萄糖、蔗糖、纤维素、山梨糖醇、甘露糖醇、葡萄糖酸内酯、次磷酸盐、硼烷、肼、甲酸、抗坏血酸和其混合物的群组的还原剂。还原剂最优选为乙醛酸。还原剂的浓度优选在0.1g/l到100g/l,更优选0.5g/l到50g/l且最优选1g/l到20g/l范围内。
无电电镀浴进一步包含至少一种Cu(II)离子的络合剂,其优选选自包含羧酸、羟基羧酸、氨基羧酸、烷醇胺、多元醇和其混合物的群组。
针对Cu(II)离子的还原剂与至少一种络合剂的尤其优选的组合为:
1.针对Cu(II)离子的作为还原剂的乙醛酸与作为络合剂的至少一种聚氨基二琥珀酸衍生物,其揭露于WO2013/050332A2中;
2.针对Cu(II)离子作为还原剂的乙醛酸与作为络合剂的i)至少一种聚氨基二琥珀酸衍生物与ii)选自由乙二胺四乙酸、N'-(2-羟乙基)-乙二胺-N,N,N'-三乙酸和N,N,N',N'-肆-(2-羟丙基)-乙二胺组成的群组的一或多种化合物的组合,其揭露于EP13161330.9中;和
3.针对Cu(II)离子作为还原剂的乙醛酸与作为络合剂的i)N,N,N′,N′-肆-(2-羟丙基)乙二胺与ii)来自乙二胺四乙酸和N'-(2-羟乙基)-乙二胺-N,N,N'-三乙酸的一或多者的组合,其揭露于EP13161418中。
无电电镀浴进一步包含氢氧根离子的来源,其选自由RbOH、CsOH和其混合物组成的群组。调节氢氧根离子的浓度以获得无电铜电镀浴的pH值,其范围优选在10与14之间且更优选在11与13.5之间。
根据本发明且在用于在阻障层顶部提供铜晶种层的方法中利用的无电电镀浴最优选实质上不含Na+和K+离子。“实质上不含”在本文中定义为并非有意地或有目的地添加到无电电镀浴中。可能存在一些少量Na+和/或K+杂质,但这并非所探寻或所需。
根据本发明且在用于在阻障层顶部提供铜晶种层的方法中利用的无电电镀浴还最优选实质上不含四烷基铵离子,例如四甲基铵离子。
在本发明的另一实施例中,除选自由RbOH、CsOH和其混合物组成的群组的氢氧根离子的至少一种来源外,所述无电电镀浴还包含Na+和/或K+离子。因此,可使用以下形式在本发明的这一实施例中提供氢氧根离子:通过选自由RbOH、CsOH和其混合物组成的群组的来源提供至少50mol%的氢氧根离子和通过将NaOH和/或KOH添加到所述无电电镀浴中提供低于50mol%的氢氧根离子。也可通过选自由RbOH、CsOH和其混合物组成的群组的氢氧根离子的来源在本发明的这一实施例中完全提供氢氧根离子,且以例如羧酸、羟基羧酸和/或氨基羧酸的钠盐和/或钾盐的形式将Na+和/或K+离子添加至所述无电电镀浴中作为Cu(II)离子的络合剂。
在根据本发明的方法的步骤(ii)中利用的无电电镀浴优选不含用于沉积铜的商用无电电镀浴中的氢氧根离子的来源中用作抗衡离子的Na+和K+离子。
当使用NaOH或KOH作为氢氧根离子的唯一来源时,铜晶种层的外表面的粗糙度过高(实例1到实例4)。当使用氢氧化四甲基铵或氢氧化四丁基铵作为氢氧根离子的唯一来源时,铜晶种层的外表面的粗糙度也过高(实例8和实例9)。
无电电镀浴任选地进一步包含至少一种稳定剂,其抑制电镀浴自身中的铜的非所需还原。至少一种稳定剂优选选自包含巯基苯并噻唑、硫脲、氰化物和/或氰化亚铁、氰钴酸盐、聚乙二醇衍生物、2,2'-联吡啶、甲基丁炔醇和丙腈的群组。
至少一种稳定剂的浓度优选在0.1mg/l到1000mg/l,更优选0.5mg/l到500mg/l且最优选1mg/l到250mg/l范围内。
在本发明的一优选实施例中,无电电镀浴进一步包含选自包含阳离子湿润剂、阴离子湿润剂、非离子湿润剂、两性湿润剂和其混合物的群组的湿润剂。
无电电镀浴最优选包含选自包含聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物、例如分支链仲醇乙氧基化物和乙氧基化苯酚或萘酚的醇烷氧基化物、例如乙氧基化脂肪酸的烷氧基化脂肪酸和其混合物的群组的一或多种非离子湿润剂。具体来说,所述非离子湿润剂在阻障层上的无电铜电镀期间降低电镀率。由此,阻障层顶部的铜晶种层的厚度分布改良,也就是说更均匀。
任选的湿润剂的浓度(或在两种或两种以上湿润剂的混合物的情况下,所有湿润剂一起的浓度)优选在0.1g/l到100g/l,更优选0.25g/l到25g/l且最优选0.5g/l到15g/l范围内。
可例如通过将衬底浸没到无电电镀浴中,通过将无电电镀浴喷涂于衬底上,并且通过将无电铜电镀浴分配于衬底上,使衬底与无电电镀浴接触。可用于进行根据本发明的方法的尤其适合的电镀工具揭露于US2012/0213914A1中。
在步骤(ii)期间,无电电镀浴优选保持在15℃到80℃,更优选20℃到60℃且最优选25℃到45℃范围内的温度下。在步骤(ii)期间,视待沉积铜晶种层的所需厚度和通过特定电镀浴组合物和电镀参数获得的电镀率而定,使衬底与无电电镀浴接触5秒到30分钟。
在本发明的一个实施例中,在步骤(ii)期间,将惰性气体导引通过无电电镀浴,提高电镀率。惰性气体优选选自氮气、氩气和其混合物。
通过在生产中在步骤(ii)之前和/或在电镀步骤(ii)之间导引氧气通过电解质来提高用于沉积铜晶种层的无电电镀浴的使用寿命。
在生产中在步骤(ii)之前和/或电镀步骤(ii)之间优选将氧气导引通过电解质和/或在步骤(ii)期间将惰性气体导引通过无电电镀浴。
在步骤(ii)中沉积的铜晶种层即使在例如10nm或甚至更小的厚度下也具有均匀厚度分布。因此,阻障层完全由铜晶种层覆盖,即使铜晶种层仅具有例如10nm或甚至更小的厚度。
此外,铜晶种层的外表面如所需为光滑的。以SQ值表示且在35℃下使用乙醛酸作为还原剂的无电铜电镀22分钟获得的光滑度优选在0.1nm到4nm,更优选0.2nm到3.9nm,且最优选0.5nm到3.8nm范围内。
以SQ值表示且在35℃下使用甲醛作为还原剂的无电铜电镀22分钟获得的光滑度优选在0.1nm到30nm,更优选1nm到28nm且最优选5nm到26nm范围内。
“SQ值”在本文中定义为表面的均方根高度。
所述SQ值可通过使用扫描原子力显微镜扫描铜晶种层的外表面获得。测定金属表面的光滑度和各别SQ值的此类方法和其应用在所属领域中已知。
相较于包含乙醛酸作为还原剂的无电铜电镀浴,自包含甲醛作为还原剂的无电铜电镀浴获得的铜晶种层的光滑度欠佳。使用甲醛作为还原剂还观测到选自由RbOH、CsOH和其混合物组成的群组的氢氧根离子的至少一种来源的技术效应。
衬底随后适于通过电镀将金属沉积于铜晶种层上。
用于在阻障层顶部提供铜晶种层的方法还适用于完全用铜填充例如双镶嵌结构的嵌入型结构,而非仅提供晶种层以在上面连续电镀例如铜的金属。自本发明的此实施例获得用铜沉积物填充的嵌入型结构。
通过电镀沉积于铜晶种层上的金属原则上可为任何可被电镀于铜晶种层上的金属或金属合金。通过电镀沉积于铜晶种层上的金属最优选为铜。用于将例如铜的金属或金属合金沉积于铜晶种层上的适合浴组合物和电镀条件在所属领域中已知。
实例
现将参考以下非限制性实例说明本发明。
通用程序
衬底材料:
在实例1到实例2、实例4到实例6、实例8以及实例9的情况下,衬底材料为呈晶圆形式的硅,所述晶圆具有附着至晶圆表面的钌阻障层,晶圆表面上在还原表面氧化物和用贵金属催化剂活化之后通过无电电镀沉积铜。
在实例3和实例7的情况下,衬底材料为呈晶圆形式的硅,所述晶圆具有附着至晶圆表面的钴阻障层,晶圆表面上在未还原表面氧化物和用贵金属催化剂活化的情况下通过无电电镀沉积铜。
在作为阻障层材料的钌上还原表面氧化物:
湿式-化学预处理方法由以下步骤组成:将包含钌阻障层的衬底浸没到由作为溶剂的二乙二醇中的作为还原剂的2g/l二甲氨基硼烷组成的溶液中(T=65℃,t=2分钟)。
无电铜电镀浴:
使用两种不同无电铜电镀浴类型。第一类型的铜电镀浴包含乙醛酸作为还原剂和烷醇胺作为络合剂。第二类型的铜电镀浴包含甲醛作为还原剂和酒石酸盐作为络合剂。
在整个实例中添加不同来源的氢氧根离子以在两种类型的铜电镀浴中获得13的pH值。
在铜沉积期间使电镀浴保持在35℃下且电镀时间为22分钟。
研究铜晶种层的表面光滑度:
使用扫描原子力显微镜(数字仪表(DigitalInstruments),装备有来自Nanosensors的尖端半径小于7nm的的NanoScope)测定铜晶种层的外表面光滑度,扫描尺寸:1×1μm(基于乙醛酸的电镀浴)和5×5μm(基于甲醛的电镀浴),以轻敲模式扫描。
通过这些测量获得SQ值,且用以下各别实例提供SQ值。
实例1(比较实例)
在还原表面氧化物之后,将铜沉积于包含钌阻障层的硅晶圆上。铜电镀浴中的氢氧根离子的唯一来源为NaOH且还原剂为乙醛酸。
铜晶种层外表面的扫描电子显微相片显示于图1中。
根据图2中所示的扫描原子力显微镜扫描图,所获得的SQ值为11.71nm。
实例2(比较实例)
在还原表面氧化物之后,将铜沉积于包含钌阻障层的硅晶圆上。在铜电镀浴中的氢氧根离子的唯一来源为NaOH且还原剂为甲醛。
铜晶种层外表面的扫描电子显微相片显示于图3中。
根据图4中所示的扫描原子力显微镜扫描图,所获得的SQ值为31.4nm。
实例3(比较实例)
在还原表面氧化物之后,将铜沉积于包含钴阻障层的硅晶圆上。在铜电镀浴中的氢氧根离子的唯一来源为NaOH且还原剂为乙醛酸。
铜晶种层外表面的扫描电子显微相片显示于图5中。
实例4(比较实例)
在还原表面氧化物之后,将铜沉积于包含钌阻障层的硅晶圆上。在铜电镀浴中的氢氧根离子的唯一来源为KOH且还原剂为甲醛。
铜晶种层外表面的扫描电子显微相片显示于图6中。
根据图7中所示的扫描原子力显微镜扫描图,所获得的SQ值为33.5nm。
实例5(本发明)
在还原表面氧化物之后,将铜沉积于包含钌阻障层的硅晶圆上。在铜电镀浴中的氢氧根离子的唯一来源为CsOH且还原剂为乙醛酸。
铜晶种层外表面的扫描电子显微相片显示于图8中。
根据图9中所示的扫描原子力显微镜扫描图,所获得的SQ值为3.67nm。
实例6(本发明)
在还原表面氧化物之后,将铜沉积于包含钌阻障层的硅晶圆上。在铜电镀浴中的氢氧根离子的唯一来源为CsOH且还原剂为甲醛。
铜晶种层外表面的扫描电子显微相片显示于图10中。
根据图11中所示的扫描原子力显微镜扫描图,所获得的SQ值为24.0nm。
实例7(本发明)
将铜沉积于包含钴阻障层的硅晶圆上。在铜电镀浴中的氢氧根离子的唯一来源为CsOH且还原剂为乙醛酸。
铜晶种层外表面的扫描电子显微相片显示于图12中。
实例8(比较实例)
在还原表面氧化物之后,将铜沉积于包含钌阻障层的硅晶圆上。在铜电镀浴中的氢氧根离子的唯一来源为氢氧化四甲基铵且还原剂为乙醛酸(根据US2004/0152303A1的实例)。
根据图13中所示的扫描原子力显微镜扫描图,所获得的SQ值为9.3nm。
实例9(比较实例)
在还原表面氧化物之后,将铜沉积于包含钌阻障层的硅晶圆上。在铜电镀浴中的氢氧根离子的唯一来源为氢氧化四丁基铵且还原剂为乙醛酸。
根据图14中所示的扫描原子力显微镜扫描图,所获得的SQ值为20.07nm。
Claims (15)
1.一种用于在阻障层顶部提供铜晶种层的方法,其依序包含以下步骤
(i)提供至少在外表面的一部分上包含阻障层的衬底,
(ii)使所述衬底与水性无电铜电镀浴接触,所述无电铜电镀浴包含
a.Cu(II)离子的水溶性来源,
b.Cu(II)离子的还原剂,
c.Cu(II)离子的至少一种络合剂和
d.选自由RbOH、CsOH和其混合物组成的群组的至少一种氢氧根离子来源。
2.根据权利要求1所述的用于在阻障层顶部提供铜晶种层的方法,其中所述衬底材料选自由硅、硅衬底上的低κ介电材料和玻璃组成的群组。
3.根据前述权利要求中任一权利要求所述的用于在阻障层顶部提供铜晶种层的方法,其中所述阻障层选自由钴、镍、钌、钨、钽、钛、铱、铑和前述的合金组成的群组。
4.根据前述权利要求中任一权利要求所述的用于在阻障层顶部提供铜晶种层的方法,其中在步骤(ii)中利用的所述无电铜电镀浴实质上不含Na+和K+离子。
5.根据前述权利要求中任一权利要求所述的用于在阻障层顶部提供铜晶种层的方法,其中在步骤(ii)中利用的所述无电铜电镀浴中的所述还原剂选自由甲醛、乙醛酸、葡萄糖、蔗糖、纤维素、山梨糖醇、甘露糖醇、葡萄糖酸内酯、次磷酸盐、硼烷、肼、甲酸、抗坏血酸和其混合物组成的群组。
6.根据前述权利要求中任一权利要求所述的用于在阻障层顶部提供铜晶种层的方法,其中在步骤(ii)中利用的所述无电铜电镀浴中的所述还原剂为乙醛酸。
7.根据前述权利要求中任一权利要求所述的用于在阻障层顶部提供铜晶种层的方法,其中在步骤(ii)中利用的所述无电铜电镀浴中的Cu(II)离子的所述络合剂选自由羧酸、羟基羧酸、氨基羧酸、烷醇胺、多元醇和其混合物组成的群组。
8.根据前述权利要求中任一权利要求所述的用于在阻障层顶部提供铜晶种层的方法,其中在步骤(ii)中利用的所述无电铜电镀浴进一步包含湿润剂,所述湿润剂选自包含阳离子湿润剂、阴离子湿润剂、非离子湿润剂、两性湿润剂和其混合物的群组。
9.根据前述权利要求中任一权利要求所述的用于在阻障层顶部提供铜晶种层的方法,其中在步骤(ii)中利用的所述无电铜电镀浴进一步包含湿润剂,所述湿润剂选自由聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物、例如分支链仲醇乙氧基化物和乙氧基化苯酚或萘酚的醇烷氧基化物、例如乙氧基化脂肪酸的烷氧基化脂肪酸和其混合物组成的群组。
10.根据权利要求8所述的用于在阻障层顶部提供铜晶种层的方法,其中在步骤(ii)中利用的所述无电铜电镀浴的所述湿润剂的浓度在0.1g/l到100g/l范围内。
11.根据前述权利要求中任一权利要求所述的用于在阻障层顶部提供铜晶种层的方法,其中所述阻障层为钌且用于在步骤(ii)之前还原表面氧化物的方式选自由使用N2/H2等离子处理和使用在溶剂中提供的还原剂处理组成的群组。
12.根据权利要求11所述的用于在阻障层顶部提供铜晶种层的方法,其中在溶剂中提供的所述还原剂选自由通过将阴极电压施加至所述溶剂原位产生的初生氢、乙醛酸、甲醛、次磷酸盐、肼、二甲氨基硼烷、三甲氨基硼烷、N-甲基吗啉基硼烷和硼氢化钠组成的群组。
13.根据权利要求11和12所述的用于在阻障层顶部提供铜晶种层的方法,其中所述溶剂选自由水、醇类、二醇醚和其混合物组成的群组。
14.根据前述权利要求中任一权利要求所述的用于在阻障层顶部提供铜晶种层的方法,其中在铜电镀之前将氧气导引通过电解质且在步骤(ii)期间将惰性气体导引通过所述无电电镀浴。
15.一种水性无电铜电镀浴,其包含
a.Cu(II)离子的来源,
b.作为Cu(II)离子的还原剂的乙醛酸,
c.Cu(II)离子的至少一种络合剂和
d.选自由RbOH、CsOH和其混合物组成的群组的氢氧根离子的至少一种来源其中所述无电铜电镀浴实质上不含Na+、K+和四烷基铵离子。
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CN117779011A (zh) * | 2024-02-23 | 2024-03-29 | 昆山一鼎工业科技有限公司 | 一种晶圆化学镀钨合金溶液、配制方法和化学镀方法 |
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KR102019222B1 (ko) * | 2018-12-14 | 2019-09-06 | 한국과학기술원 | 다공성 포르피린 고분자에 흡착된 귀금속 회수를 위한 무전해 도금용 도금액 및 무전해 도금방법 |
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JP6498187B2 (ja) | 2019-04-10 |
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US10077498B2 (en) | 2018-09-18 |
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TWI646216B (zh) | 2019-01-01 |
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