TWI614373B - 於阻障層上沈積銅晶種層的方法 - Google Patents
於阻障層上沈積銅晶種層的方法 Download PDFInfo
- Publication number
- TWI614373B TWI614373B TW103133354A TW103133354A TWI614373B TW I614373 B TWI614373 B TW I614373B TW 103133354 A TW103133354 A TW 103133354A TW 103133354 A TW103133354 A TW 103133354A TW I614373 B TWI614373 B TW I614373B
- Authority
- TW
- Taiwan
- Prior art keywords
- barrier layer
- seed layer
- group
- copper seed
- ions
- Prior art date
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 153
- 239000010949 copper Substances 0.000 title claims abstract description 153
- 230000004888 barrier function Effects 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000000151 deposition Methods 0.000 title description 13
- -1 Cu(II) ions Chemical class 0.000 claims abstract description 78
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 55
- 238000007747 plating Methods 0.000 claims abstract description 55
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 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 8
- 238000007772 electroless plating Methods 0.000 claims description 47
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 47
- 239000000758 substrate Substances 0.000 claims description 32
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 23
- 239000000080 wetting agent Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 238000009713 electroplating Methods 0.000 claims description 20
- 239000003906 humectant Substances 0.000 claims description 17
- 229910052715 tantalum Inorganic materials 0.000 claims description 15
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 15
- 229910052732 germanium Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 239000003989 dielectric material Substances 0.000 claims description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229910001414 potassium ion Inorganic materials 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000011521 glass Substances 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 150000004780 naphthols Chemical class 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 150000003333 secondary alcohols Chemical class 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 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
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-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
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 2
- 229960003681 gluconolactone Drugs 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 235000010356 sorbitol Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 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
- HOLGGDCHRDNGKZ-UHFFFAOYSA-N CN1C(COCC1)B Chemical compound CN1C(COCC1)B HOLGGDCHRDNGKZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000009832 plasma treatment Methods 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 7
- 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
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004630 atomic force microscopy Methods 0.000 description 14
- 238000001878 scanning electron micrograph Methods 0.000 description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JJFNJZGXHWYGMQ-UHFFFAOYSA-N [Ni].B#[Co] Chemical compound [Ni].B#[Co] JJFNJZGXHWYGMQ-UHFFFAOYSA-N 0.000 description 1
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001412 amines Chemical class 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
- 239000002981 blocking agent Substances 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate 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
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000386 microscopy 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
- WOFPPJOZXUTRAU-UHFFFAOYSA-N octan-4-ol Chemical compound CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 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
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 238000007704 wet chemistry method 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
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- 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
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Abstract
本發明係關於一種在阻障層之頂部提供銅晶種層之方法,其中該晶種層自水性無電銅電鍍浴沈積於該阻障層上,該無電銅電鍍浴包含Cu(II)離子之水溶性來源、Cu(II)離子之還原劑、Cu(II)離子之至少一種錯合劑及選自由RbOH、CsOH及其混合物組成之群的至少一種氫氧根離子來源。所得銅晶種層具有均勻厚度分佈及光滑外表面,此皆為所需特性。
Description
本發明係關於一種在充當連續電鍍之電鍍基底之阻障層上沈積銅晶種層之方法。根據本發明之方法尤其適用於微晶片及其類似物之製造中的雙鑲嵌電鍍。
金屬之電鍍,尤其銅電鍍在由諸如釕及鈷之典型阻障材料製成之基板表面之情況下,需要導電晶種層。此類晶種層原則上可由任何種類之導電材料組成。然而,由於銅之固有電導率較高,因此銅晶種層較佳。
該晶種層必須滿足若干要求,諸如對底層阻障層及藉由電鍍沈積於該晶種層頂部之金屬的足夠黏附力。此外,晶種層應具有均勻(狹窄)厚度分佈及光滑外表面。此類要求在微晶片及其類似物之製造中尤其重要,其中需要塗佈有此類銅晶種層之嵌入型結構之尺寸可低至奈米範圍內。
在由釕製成之阻障層上電鍍銅晶種層之方法揭示於US 7,998,859 B2及US 7,470,617 B2中。兩種方法皆利用包含還原劑之水溶液以在無電銅電鍍之前自釕阻障層移除非所需表面氧化物。兩種方法進一步利用標準無電銅電鍍浴組合物,其包含NaOH或KOH作為氫氧根離子之唯一來源。銅晶種層之外表面的粗糙度在兩種情況下皆過高(比較
實例1至比較實例4)。
因此,需要提供藉由無電電鍍沈積於阻障層上之薄銅層,其產生外表面具有改良光滑度之銅晶種層。
本發明之目標為提供一種於阻障層上沈積銅晶種層以供連續電鍍之方法,該阻障層具有均勻厚度分佈及光滑外表面。
藉由一種於阻障層之頂部提供銅晶種層之方法解決此目標,該方法依序包含以下步驟:(i)提供至少在外表面之一部分上包含阻障層之基板,(ii)使該基板與水性無電銅電鍍浴接觸,該無電銅電鍍浴包含a. Cu(II)離子之水溶性來源,b. Cu(II)離子之還原劑,c. Cu(II)離子之至少一種錯合劑及d. 選自由RbOH、CsOH及其混合物組成之群的至少一種氫氧根離子來源。
藉由根據本發明之方法獲得之阻障層頂部的銅晶種層提供對底層阻障層及電鍍於該銅晶種層上之金屬層之足夠黏附力。此外,銅晶種層具有均勻厚度分佈及所需光滑表面。在藉由無電電鍍將銅晶種層沈積於阻障層上之前,不需用貴金屬活化劑活化該阻障層。
圖1展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描電子顯微相片,該無電電鍍浴含有NaOH作為氫氧根離子之唯一來源及乙醛酸作為還原劑(實例1(比較例))。
圖2展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描原子
力顯微(AFM)相片,該無電電鍍浴含有NaOH作為氫氧根離子之唯一來源及乙醛酸作為還原劑(實例1(比較例))。
圖3展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描電子顯微相片,該無電電鍍浴含有NaOH作為氫氧根離子之唯一來源及甲醛作為還原劑(實例2(比較例))。
圖4展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描原子力顯微(AFM)相片,該無電電鍍浴含有NaOH作為氫氧根離子之唯一來源及甲醛作為還原劑(實例2(比較例))。
圖5展示於鈷阻障層上自無電電鍍浴獲得之銅晶種層之掃描電子顯微相片,該無電電鍍浴含有NaOH作為氫氧根離子之唯一來源及乙醛酸作為還原劑(實例3(比較例))。
圖6展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描電子顯微相片,該無電電鍍浴含有KOH作為氫氧根離子之唯一來源及甲醛作為還原劑(實例4(比較例))。
圖7展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描原子力顯微(AFM)相片,該無電電鍍浴含有KOH作為氫氧根離子之唯一來源及甲醛作為還原劑(實例4(比較例))。
圖8展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描電子顯微相片,該無電電鍍浴含有CsOH作為氫氧根離子之唯一來源及乙醛酸作為還原劑(實例5(本發明))。
圖9展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描原子力顯微(AFM)相片,該無電電鍍浴含有CsOH作為氫氧根離子之唯一來源及乙醛酸作為還原劑(實例5(本發明))。
圖10展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描電子顯微相片,該無電電鍍浴含有CsOH作為氫氧根離子之唯一來源及甲醛作為還原劑(實例6(本發明))。
圖11展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描原子力顯微(AFM)相片,該無電電鍍浴含有CsOH作為氫氧根離子之唯一來源及甲醛作為還原劑(實例6(本發明))。
圖12展示於鈷阻障層上自無電電鍍浴獲得之銅晶種層之掃描電子顯微相片,該無電電鍍浴含有CsOH作為氫氧根離子之唯一來源及乙醛酸作為還原劑(實例7(本發明))。
圖13展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描原子力顯微(AFM)相片,該無電電鍍浴含有氫氧化四甲銨作為氫氧根離子之唯一來源及乙醛酸作為還原劑(實例8(比較例))。
圖14展示於釕阻障層上自無電電鍍浴獲得之銅晶種層之掃描原子力顯微(AFM)相片,該無電電鍍浴含有氫氧化四丁基銨作為氫氧根離子之唯一來源及乙醛酸作為還原劑(實例9(比較例))。
適用於在根據本發明之阻障層之頂部提供銅晶種層之方法的基板材料較佳選自矽、矽基板上之低κ介電材料及玻璃。由此類材料製成之電子裝置包含微晶片、玻璃插入件及其類似物。此類基板材料中之嵌入型結構需要塗佈或填充有通常藉由電鍍沈積之金屬。最相關之金屬為經電鍍之銅。
於根據本發明之阻障層之頂部提供銅晶種層之方法的一個特定應用為將金屬電鍍至極其精細的嵌入型結構中,該嵌入型結構被蝕刻至矽基板、矽基板上之低κ介電材料中。典型的低κ介電材料在此項技術中已知且包含氟摻雜之二氧化矽、碳摻雜之二氧化矽、多孔二氧化矽、多孔碳摻雜之二氧化矽、聚醯亞胺、聚降莰烯、苯并環丁烷、PTFE及旋塗式基於聚矽氧之聚合介電質,諸如氫-倍半氧矽烷及甲基-倍半氧矽烷。
此類極精細之嵌入型結構可為盲孔(僅具有一個開口)、穿孔(在
兩側均具有開口)以及溝槽(線型圖案及其類似物)。此類嵌入型結構通常具有例如14nm至幾百微米或甚至毫米範圍內之幾何尺寸。
此特定應用可分為1. 雙鑲嵌應用,其中嵌入型結構形成於矽及/或低κ介電材料中且具有在奈米或較低微米範圍內之開口尺寸。銅晶種層可具有1nm至20nm範圍內之厚度及2. 矽穿孔(TSV)之填充物,其為在矽及/或矽基板上之低κ介電材料中之盲孔。TSV之開口在微米範圍內且銅晶種層可具有高達幾百奈米或甚至1微米或1微米以上之厚度。
於阻障層之頂部之銅晶種層之另一特定應用在顯示器之製造中,諸如基於液晶之顯示器,其中玻璃基板塗佈有一或多個金屬阻障層。可藉由於一或多個阻障層上沈積具有光滑外表面之銅晶種層,繼而於其上電鍍諸如銅之金屬來形成電路。
所有此等應用均需要銅晶種層之均勻厚度分佈及光滑外表面。
在許多情況下,必須抑制該經電鍍金屬進入基板材料中或基板材料進入經電鍍金屬中之非所需擴散及相關過程以便獲得及/或維持最終電子裝置之所需特性。因此,藉助於一或多個阻障層分隔經電鍍金屬,該等阻障層藉由以下方法沈積:諸如化學氣相沈積(CVD)、物理氣相沈積(PVD)及原子層沈積(ALD)之氣相方法及前述之電漿增強型方法或諸如無電電鍍之濕式化學製程。在兩個或兩個以上個別阻障層材料之堆疊的情況下,僅最外部阻障層將與無電銅電鍍浴接觸。在兩個或兩個以上個別阻障層之堆疊的情況下,單種阻障層材料或最外部阻障層材料係選自鈷、鎳、釕、鎢、鉬、鉭、鈦、銥、銠及前述之合金。
該「前述之合金」包含諸如氮化鎢、氮化鉭及氮化鈷(諸如Co4N)之氮化物以及磷化物及硼化物,諸如鈷-及鎳-磷或-硼合金、三元鈷-
及鎳-磷合金及三元鈷-及鎳-硼合金(例如,Ni-Mo-P、Ni-W-P、Co-Mo-P、Co-W-P、Co-W-B)。
該阻障層或最外部阻障層之厚度在若干阻障層之堆疊的情況下通常具有1nm至20nm範圍內之厚度。
自阻障層移除非所需表面氧化物:
若在個別阻障層之堆疊之情況下單種阻障層材料或最外部阻障層材料為釕層,可能需要在藉由無電電鍍沈積銅晶種層之前移除存在於該阻障層材料之外表面頂部的表面氧化物,因為其可能阻止銅晶種層完全覆蓋在該阻障層之整個外表面上。
可藉由使用例如N2/H2電漿處理釕表面及/或藉由使用在溶劑中提供之還原劑處理釕表面,在步驟(ii)之前充分地移除該等表面氧化物。
自阻障層濕式-化學移除非所需表面氧化物:
用於充分移除該等表面氧化物的溶劑中之適合還原劑選自包含乙醛酸、甲醛、次磷酸鹽、肼、二甲胺基硼烷、三甲胺硼烷、N-甲基嗎啉基硼烷及硼氫化鈉之群。該還原劑於溶劑中之濃度較佳在0.001mol/l至10mol/l,更佳0.005mol/l至5mol/l且最佳0.01mol/l至2mol/l範圍內。
溶劑較佳選自包含水、諸如異丙醇之醇類、諸如二乙二醇之二醇醚類及其混合物之群。水與前述有機溶劑中之一或多者之混合物較佳包含50重量%的水且更佳低於50重量%之水。當利用該水-(有機)溶劑代替純水或含有超過50重量%水之水-(有機)溶劑混合物時,還原劑之穩定性提高。
具有釕阻障層之基板較佳與溶劑中之該還原劑接觸30秒至20分鐘且更佳1分鐘至10分鐘。在該製程步驟期間還原劑-溶劑混合物之溫度較佳保持在20℃至90℃且更佳50℃至90℃範圍內。
該還原劑-溶劑混合物較佳包含濕潤劑,諸如陽離子濕潤劑、陰離子濕潤劑、非離子濕潤劑、兩性濕潤劑及其混合物。此種類型之濕潤劑例如揭示於US 7,998,859 B2中。
濕潤劑於還原劑-溶劑混合物中之濃度較佳在0.1g/l至100g/l,更佳0.25g/l至25g/l且最佳0.5g/l至15g/l範圍內。
用於充分移除釕阻障層之外表面上之非所需表面氧化物的另一種適合濕式-化學方法為用初生氫處理釕阻障層,該初生氫藉由在溶劑中將陰極電流施加至與該溶劑接觸之基板就地生成。在此實施例中,初生氫充當溶劑中所提供之還原劑。
施加至基板之電壓較佳在0.5V至20V,更佳1V至15V且最佳2V至10V範圍內,且將其保持1秒至360秒,更佳10秒至180秒且最佳20秒至120秒。溶劑較佳選自包含水、諸如異丙醇之醇類、諸如二乙二醇之二醇醚及其混合物之群。
在此製程步驟期間將含有就地形成之初生氫的溶劑保持在10℃至80℃,更佳15℃至60℃且最佳20℃至40℃範圍內之溫度下。
溶劑較佳包含選自陽離子濕潤劑、陰離子濕潤劑、非離子濕潤劑、兩性濕潤劑及其混合物之濕潤劑。溶劑更佳包含非離子濕潤劑或兩種或兩種以上非離子濕潤劑之混合物。溶劑最佳包含選自包含聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物、諸如分支鏈二級醇乙氧基化物及乙氧基化酚或萘酚之醇烷氧基化物、諸如乙氧基化脂肪酸之烷氧基化脂肪酸及其混合物之群的非離子濕潤劑。該非離子濕潤劑尤其支持用初生氫作為還原劑之表面氧化物之所需移除。
濕潤劑於溶劑中之濃度或所有濕潤劑一起(在利用超過一種濕潤劑之情形中)之濃度較佳在0.5g/l至100g/l,更佳1g/l至25g/l且最佳5g/l至15g/l範圍內。
在本發明之一個實施例中,組合該用於還原釕阻障層頂部之表
面氧化物之方式中之兩者或兩者以上。使用例如水之沖洗液體之沖洗步驟可在步驟(ii)之前分離該等用於還原表面氧化物之該手段。沖洗液體可進一步包含較佳選自包含聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物、諸如分支鏈二級醇乙氧基化物及乙氧基化酚或萘酚之醇烷氧基化物、諸如乙氧基化脂肪酸之烷氧基化脂肪酸及其混合物之群的非離子濕潤劑。
視情況選用之非離子濕潤劑沖洗液體中之濃度或所有濕潤劑一起(在利用超過一種非離子濕潤劑之情形中)之濃度較佳在0.5g/l至100g/l,更佳1g/l至25g/l且最佳5g/l至15g/l範圍內。
在根據本發明之方法的步驟(ii)之前,基板可例如用水沖洗。
不適於藉由無電(自催化)電鍍在上面沈積銅層之阻障層材料在根據本發明之方法的步驟(ii)之前需要各別活化。該活化在此項技術中已知且例如用於製造印刷電路板及其類似物。因此,不適於藉由無電式(自催化)電鍍在上面沈積銅層之阻障層材料可例如藉由浸沒電鍍將諸如鈀之貴金屬沈積於該阻障層材料上來活化,該阻障層材料隨後適於藉由無電(自催化)電鍍在上面沈積銅。
於阻障層上之銅晶種層之無電電鍍:
此類阻障層之一個特定缺點為其電導率通常比例如銅之電導率低得多。因此,連續電鍍需要與阻障層材料相比具有提高之電導率的銅晶種層。
該銅晶種層之厚度針對諸如矽穿孔之填充物及顯示器之製造較佳在50nm至2μm範圍內。在雙鑲嵌應用之情況下,銅晶種層之厚度較佳在1nm至20nm範圍內。
在根據本發明之方法的步驟(ii)中,藉由無電電鍍將銅晶種層沈積於阻障層(或在兩種或兩種以上個別阻障層之堆疊的情況下最外部阻障層)上。
「無電電鍍」意謂「自催化電鍍」。因此,在步驟(ii)中利用之銅電鍍浴包含針對Cu(II)離子之還原劑。
在根據本發明之方法中利用的無電銅電鍍浴較佳為水性電鍍浴,亦即溶劑為水。
Cu(II)離子之水溶性來源較佳係選自包含硫酸銅、氯化銅、硝酸銅、乙酸銅、甲烷磺酸銅、氫氧化銅、甲酸銅及其水合物之群。無電電鍍浴中之Cu(II)離子之濃度較佳在0.05g/l至20g/l,更佳0.1g/l至10g/l且最佳0.2g/l至6g/l範圍內。
無電電鍍浴進一步含有選自包含甲醛、乙醛酸、葡萄糖、蔗糖、纖維素、山梨糖醇、甘露糖醇、葡萄糖酸內酯、次磷酸鹽、硼烷、肼、甲酸、抗壞血酸及其混合物之群的還原劑。還原劑最佳為乙醛酸。還原劑之濃度較佳在0.1g/l至100g/l,更佳0.5g/l至50g/l且最佳1g/l至20g/l範圍內。
無電電鍍浴進一步包含至少一種Cu(II)離子之錯合劑,其較佳選自包含羧酸、羥基羧酸、胺基羧酸、烷醇胺、多元醇及其混合物之群。
針對Cu(II)離子之還原劑與至少一種錯合劑之尤其較佳的組合為:1. 針對Cu(II)離子的作為還原劑之乙醛酸與作為錯合劑之至少一種聚胺基二琥珀酸衍生物,其揭示於WO 2013/050332 A2中;2. 針對Cu(II)離子作為還原劑之乙醛酸與作為錯合劑之i)至少一種聚胺基二琥珀酸衍生物與ii)選自由乙二胺四乙酸、N'-(2-羥乙基)-乙二胺-N,N,N'-三乙酸及N,N,N',N'-肆-(2-羥丙基)-乙二胺組成之群的一或多種化合物的組合,其揭示於EP 13161330.9中;及3. 針對Cu(II)離子作為還原劑之乙醛酸與作為錯合劑之i)N,N,N',N'-肆-(2-羥丙基)乙二胺與ii)來自乙二胺四乙酸及N'-(2-羥乙
基)-乙二胺-N,N,N'-三乙酸之一或多者的組合,其揭示於EP 13161418中。
無電電鍍浴進一步包含氫氧根離子之來源,其係選自由RbOH、CsOH及其混合物組成之群。調節氫氧根離子之濃度以獲得無電銅電鍍浴之pH值,其範圍較佳在10與14之間且更佳在11與13.5之間。
根據本發明且在用於在阻障層頂部提供銅晶種層之方法中利用的無電電鍍浴最佳實質上不含Na+及K+離子。「實質上不含」在本文中定義為並非有意地或有目的地添加至無電電鍍浴中。可能存在一些少量Na+及/或K+雜質,但此並非所探尋或所需。
根據本發明且在用於在阻障層頂部提供銅晶種層之方法中利用的無電電鍍浴亦最佳實質上不含四烷基銨離子,諸如四甲基銨離子。
在本發明之另一實施例中,除選自由RbOH、CsOH及其混合物組成之群的氫氧根離子之至少一種來源外,該無電電鍍浴亦包含Na+及/或K+離子。因此,可使用以下形式在本發明之此實施例中提供氫氧根離子:藉由選自由RbOH、CsOH及其混合物組成之群的來源提供至少50mol%的氫氧根離子及藉由將NaOH及/或KOH添加至該無電電鍍浴中提供低於50mol%的氫氧根離子。亦可藉由選自由RbOH、CsOH及其混合物組成之群的氫氧根離子之來源在本發明之此實施例中完全提供氫氧根離子,且以例如羧酸、羥基羧酸及/或胺基羧酸之鈉鹽及/或鉀鹽之形式將Na+及/或K+離子添加至該無電電鍍浴中作為Cu(II)離子之錯合劑。
在根據本發明之方法的步驟(ii)中利用的無電電鍍浴較佳不含用於沈積銅之商用無電電鍍浴中之氫氧根離子之來源中用作相對離子的Na+及K+離子。
當使用NaOH或KOH作為氫氧根離子之唯一來源時,銅晶種層之外表面的粗糙度過高(實例1至實例4)。當使用氫氧化四甲基銨或氫氧
化四丁基銨作為氫氧根離子之唯一來源時,銅晶種層之外表面的粗糙度亦過高(實例8及實例9)。
無電電鍍浴視情況進一步包含至少一種穩定劑,其抑制電鍍浴自身中之銅的非所需還原。至少一種穩定劑較佳係選自包含統基苯并噻唑、硫脲、氰化物及/或亞鐵氰化物、氰鈷酸鹽、聚乙二醇衍生物、2,2'-聯吡啶、甲基丁炔醇及丙腈之群。
至少一種穩定劑之濃度較佳在0.1mg/l至1000mg/l,更佳0.5mg/l至500mg/l且最佳1mg/l至250mg/l範圍內。
在本發明之一較佳實施例中,無電電鍍浴進一步包含選自包含陽離子濕潤劑、陰離子濕潤劑、非離子濕潤劑、兩性濕潤劑及其混合物之群的濕潤劑。
無電電鍍浴最佳包含選自包含聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物、諸如分支鏈二級醇乙氧基化物及乙氧基化酚或萘酚之醇烷氧基化物、諸如乙氧基化脂肪酸之烷氧基化脂肪酸及其混合物之群的一或多種非離子濕潤劑。特定言之,該等非離子濕潤劑在阻障層上之無電銅電鍍期間降低電鍍率。藉此,阻障層頂部之銅晶種層之厚度分佈改良,亦即更均勻。
視情況選用之濕潤劑之濃度(或在兩種或兩種以上濕潤劑之混合物的情況下,所有濕潤劑一起之濃度)較佳在0.1g/l至100g/l,更佳0.25g/l至25g/l且最佳0.5g/l至15g/l範圍內。
可例如藉由將基板浸沒至無電電鍍浴中,藉由將無電電鍍浴噴塗於基板上,及藉由將無電銅電鍍浴分配於基板上,使基板與無電電鍍浴接觸。可用於進行根據本發明之方法的尤其適合的電鍍工具揭示於US 2012/0213914 A1中。
在步驟(ii)期間,無電電鍍浴較佳保持在15℃至80℃,更佳20℃至60℃且最佳25℃至45℃範圍內之溫度下。在步驟(ii)期間,視待沈
積銅晶種層之所需厚度及藉由特定電鍍浴組合物及電鍍參數獲得的電鍍率而定,使基板與無電電鍍浴接觸5秒至30分鐘。
在本發明之一個實施例中,在步驟(ii)期間,將惰性氣體導引通過無電電鍍浴,提高電鍍率。惰性氣體較佳係選自氮氣、氬氣及其混合物。
藉由在生產中之步驟(ii)之前及/或在電鍍步驟(ii)之間導引氧氣通過電解質來延長用於沈積銅晶種層之無電電鍍浴之使用壽命。
在生產中之步驟(ii)之前及/或電鍍步驟(ii)之間較佳將氧氣導引通過電解質及/或在步驟(ii)期間將惰性氣體導引通過無電電鍍浴。
在步驟(ii)中沈積的銅晶種層即使在例如10nm或甚至更小之厚度下亦具有均勻厚度分佈。因此,阻障層完全由銅晶種層覆蓋,即使銅晶種層僅具有例如10nm或甚至更小之厚度。
此外,銅晶種層之外表面如所需為光滑的。以SQ值表示且在35℃下使用乙醛酸作為還原劑之無電銅電鍍22分鐘獲得之光滑度較佳在0.1nm至4nm,更佳0.2nm至3.9nm,且最佳0.5nm至3.8nm範圍內。
以SQ值表示且在35℃下使用甲醛作為還原劑之無電銅電鍍22分鐘獲得之光滑度較佳在0.1nm至30nm,更佳1nm至28nm且最佳5nm至26nm範圍內。
「SQ值」在本文中定義為表面之均方根高度。
該SQ值可藉由使用掃描原子力顯微鏡掃描銅晶種層之外表面獲得。測定金屬表面之光滑度及各別SQ值之此類方法及其應用在此項技術中已知。
相較於包含乙醛酸作為還原劑之無電銅電鍍浴,自包含甲醛作為還原劑之無電銅電鍍浴獲得之銅晶種層的光滑度欠佳。使用甲醛作為還原劑亦觀測到選自由RbOH、CsOH及其混合物組成之群的氫氧根離子之至少一種來源之技術作用。
基板隨後適於藉由電鍍將金屬沈積於銅晶種層上。
用於在阻障層頂部提供銅晶種層之方法亦適用於完全用銅填充諸如雙鑲嵌結構之嵌入型結構,而非僅提供晶種層以在其上連續電鍍諸如銅之金屬。自本發明之此實施例獲得用銅沈積物填充之嵌入型結構。
藉由電鍍沈積於銅晶種層上之金屬原則上可為任何可被電鍍於銅晶種層上之金屬或金屬合金。藉由電鍍沈積於銅晶種層上之金屬最佳為銅。用於將諸如銅之金屬或金屬合金沈積於銅晶種層上之適合浴組合物及電鍍條件在此項技術中已知。
現將參考以下非限制性實例說明本發明。
基板材料:
在實例1至實例2、實例4至實例6、實例8及實例9之情況下,基板材料為呈晶圓形式之矽,該晶圓具有附著至晶圓表面之釕阻障層,晶圓表面上在還原表面氧化物及用貴金屬催化劑活化之後藉由無電電鍍沈積銅。
在實例3及實例7之情況下,基板材料為呈晶圓形式之矽,該晶圓具有附著至晶圓表面之鈷阻障層,晶圓表面上在未還原表面氧化物及用貴金屬催化劑活化之情況下藉由無電電鍍沈積銅。
在作為阻障層材料之釕上還原表面氧化物:
濕式-化學預處理方法由以下步驟組成:將包含釕阻障層之基板浸沒至由作為溶劑之二乙二醇中之作為還原劑的2g/l二甲胺硼烷組成之溶液中(T=65℃,t=2分鐘)。
無電銅電鍍浴:
使用兩種不同無電銅電鍍浴類型。第一類型之銅電鍍浴包含乙
醛酸作為還原劑及烷醇胺作為錯合劑。第二類型之銅電鍍浴包含甲醛作為還原劑及酒石酸鹽作為錯合劑。
在整個實例中添加不同來源之氫氧根離子以在兩種類型之銅電鍍浴中獲得13之pH值。
在銅沈積期間使電鍍浴保持在35℃下且電鍍時間為22分鐘。
研究銅晶種層之表面光滑度:
使用掃描原子力顯微鏡(Digital Instruments,裝備有來自Nanosensors之尖端半徑小於7nm之PointProbe®的NanoScope)測定銅晶種層之外表面光滑度,掃描尺寸:1×1μm(基於乙醛酸之電鍍浴)及5×5μm(基於甲醛之電鍍浴),以輕敲模式掃描。
藉由此等量測獲得SQ值,且用以下各別實例提供SQ值。
在還原表面氧化物之後,將銅沈積於包含釕阻障層之矽晶圓上。銅電鍍浴中之氫氧根離子之唯一來源為NaOH且還原劑為乙醛酸。
銅晶種層外表面之掃描電子顯微相片顯示於圖1中。
根據圖2中所示之掃描原子力顯微鏡掃描圖,所獲得之SQ值為11.71nm。
在還原表面氧化物之後,將銅沈積於包含釕阻障層之矽晶圓上。在銅電鍍浴中之氫氧根離子之唯一來源為NaOH且還原劑為甲醛。
銅晶種層外表面之掃描電子顯微相片顯示於圖3中。
根據圖4中所示之掃描原子力顯微鏡掃描圖,所獲得之SQ值為31.4nm。
在還原表面氧化物之後,將銅沈積於包含鈷阻障層之矽晶圓上。在銅電鍍浴中之氫氧根離子之唯一來源為NaOH且還原劑為乙醛酸。
銅晶種層外表面之掃描電子顯微相片顯示於圖5中。
在還原表面氧化物之後,將銅沈積於包含釕阻障層之矽晶圓上。在銅電鍍浴中之氫氧根離子之唯一來源為KOH且還原劑為甲醛。
銅晶種層外表面之掃描電子顯微相片顯示於圖6中。
根據圖7中所示之掃描原子力顯微鏡掃描圖,所獲得之SQ值為33.5nm。
在還原表面氧化物之後,將銅沈積於包含釕阻障層之矽晶圓上。在銅電鍍浴中之氫氧根離子之唯一來源為CsOH且還原劑為乙醛酸。
銅晶種層外表面之掃描電子顯微相片顯示於圖8中。
根據圖9中所示之掃描原子力顯微鏡掃描圖,所獲得之SQ值為3.67nm。
在還原表面氧化物之後,將銅沈積於包含釕阻障層之矽晶圓上。在銅電鍍浴中之氫氧根離子之唯一來源為CsOH且還原劑為甲醛。
銅晶種層外表面之掃描電子顯微相片顯示於圖10中。
根據圖11中所示之掃描原子力顯微鏡掃描圖,所獲得之SQ值為24.0nm。
將銅沈積於包含鈷阻障層之矽晶圓上。在銅電鍍浴中之氫氧根
離子之唯一來源為CsOH且還原劑為乙醛酸。
銅晶種層外表面之掃描電子顯微相片顯示於圖12中。
在還原表面氧化物之後,將銅沈積於包含釕阻障層之矽晶圓上。在銅電鍍浴中之氫氧根離子之唯一來源為氫氧化四甲基銨且還原劑為乙醛酸(根據US 2004/0152303 A1之實例)。
根據圖13中所示之掃描原子力顯微鏡掃描圖,所獲得之SQ值為9.3nm。
在還原表面氧化物之後,將銅沈積於包含釕阻障層之矽晶圓上。在銅電鍍浴中之氫氧根離子之唯一來源為氫氧化四丁基銨且還原劑為乙醛酸。
根據圖14中所示之掃描原子力顯微鏡掃描圖,所獲得之SQ值為20.07nm。
Claims (15)
- 一種用於在阻障層頂部提供銅晶種層之方法,其依序包含以下步驟(i)提供至少在外表面之一部分上包含阻障層之基板,(ii)使該基板與水性無電銅電鍍浴接觸,該無電銅電鍍浴包含a. Cu(II)離子之水溶性來源,b. Cu(II)離子之還原劑,c. Cu(II)離子之至少一種錯合劑及d. 選自由RbOH、CsOH及其混合物組成之群的至少一種氫氧根離子來源。
- 如請求項1之用於在阻障層頂部提供銅晶種層之方法,其中該基板材料係選自由矽、矽基板上之低κ介電材料及玻璃組成之群。
- 如請求項1之用於在阻障層頂部提供銅晶種層之方法,其中該阻障層係選自由鈷、鎳、釕、鎢、鉭、鈦、銥、銠及前述之合金組成之群。
- 如請求項1之用於在阻障層頂部提供銅晶種層之方法,其中在步驟(ii)中利用的該無電銅電鍍浴實質上不含Na+及K+離子。
- 如請求項1之用於在阻障層頂部提供銅晶種層的方法,其中在步驟(ii)中利用之該無電銅電鍍浴中之該還原劑係選自由甲醛、乙醛酸、葡萄糖、蔗糖、纖維素、山梨糖醇、甘露糖醇、葡萄糖酸內酯、次磷酸鹽、硼烷、肼、甲酸、抗壞血酸及其混合物組成之群。
- 如請求項1之用於在阻障層頂部提供銅晶種層之方法,其中在步驟(ii)中利用的該無電銅電鍍浴中之該還原劑為乙醛酸。
- 如請求項1之用於在阻障層頂部提供銅晶種層之方法,其中在步 驟(ii)中利用的該無電銅電鍍浴中之Cu(II)離子的該錯合劑係選自由羧酸、羥基羧酸、胺基羧酸、烷醇胺、多元醇及其混合物組成之群。
- 如請求項1之用於在阻障層頂部提供銅晶種層之方法,其中在步驟(ii)中利用的該無電銅電鍍浴進一步包含濕潤劑,該濕潤劑係選自包含陽離子濕潤劑、陰離子濕潤劑、非離子濕潤劑、兩性濕潤劑及其混合物之群。
- 如請求項1之用於在阻障層頂部提供銅晶種層之方法,其中在步驟(ii)中利用的該無電銅電鍍浴進一步包含濕潤劑,該濕潤劑係選自由聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物、諸如分支鏈二級醇乙氧基化物及乙氧基化酚或萘酚之醇烷氧基化物、諸如乙氧基化脂肪酸之烷氧基化脂肪酸及其混合物組成之群。
- 如請求項8或9之用於在阻障層頂部提供銅晶種層之方法,其中在步驟(ii)中利用的該無電銅電鍍浴之該濕潤劑之濃度在0.1g/l至100g/l範圍內。
- 如請求項1之用於在阻障層頂部提供銅晶種層之方法,其中該阻障層為釕且用於在步驟(ii)之前還原表面氧化物之方式係選自由使用N2/H2電漿處理及使用在溶劑中提供之還原劑處理組成之群。
- 如請求項11之用於在阻障層頂部提供銅晶種層之方法,其中在溶劑中提供的該還原劑係選自由藉由將陰極電壓施加至該溶劑就地產生之初生氫、乙醛酸、甲醛、次磷酸鹽、肼、二甲胺基硼烷、三甲胺硼烷、N-甲基嗎啉基硼烷及硼氫化鈉組成之群。
- 如請求項11之用於在阻障層頂部提供銅晶種層之方法,其中該溶劑係選自由水、醇類、二醇醚類及其混合物組成之群。
- 如請求項1之用於在阻障層頂部提供銅晶種層之方法,其中在銅電鍍之前將氧氣導引通過電解質且在步驟(ii)期間將惰性氣體導引通過該無電電鍍浴。
- 一種水性無電銅電鍍浴,其包含a. Cu(II)離子之來源,b. 作為Cu(II)離子之還原劑之乙醛酸,c. Cu(II)離子之至少一種錯合劑及d. 選自由RbOH、CsOH及其混合物組成之群的至少一種氫氧根離子來源其中該無電銅電鍍浴實質上不含Na+、K+及四烷基銨離子。
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US10077498B2 (en) | 2013-09-25 | 2018-09-18 | Atotech Deutschland Gmbh | Method for depositing a copper seed layer onto a barrier layer and copper plating bath |
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US10077498B2 (en) | 2018-09-18 |
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