TWI445847B - 於半導體上鍍覆銅 - Google Patents
於半導體上鍍覆銅 Download PDFInfo
- Publication number
- TWI445847B TWI445847B TW101113558A TW101113558A TWI445847B TW I445847 B TWI445847 B TW I445847B TW 101113558 A TW101113558 A TW 101113558A TW 101113558 A TW101113558 A TW 101113558A TW I445847 B TWI445847 B TW I445847B
- Authority
- TW
- Taiwan
- Prior art keywords
- copper
- plating
- layer
- wafer
- semiconductor
- Prior art date
Links
- 239000010949 copper Substances 0.000 title claims description 130
- 238000007747 plating Methods 0.000 title claims description 129
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 125
- 229910052802 copper Inorganic materials 0.000 title claims description 125
- 239000004065 semiconductor Substances 0.000 title claims description 82
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 82
- 239000000203 mixture Substances 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 62
- 229910052751 metal Inorganic materials 0.000 claims description 57
- 239000002184 metal Substances 0.000 claims description 57
- 229910052759 nickel Inorganic materials 0.000 claims description 43
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 22
- 229910001431 copper ion Inorganic materials 0.000 claims description 22
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 22
- 238000000151 deposition Methods 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical group 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims 1
- 238000005476 soldering Methods 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 99
- 239000002253 acid Substances 0.000 description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 230000008021 deposition Effects 0.000 description 17
- -1 iron Chemical class 0.000 description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 230000003667 anti-reflective effect Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000001465 metallisation Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000005749 Copper compound Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 150000001880 copper compounds Chemical class 0.000 description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 150000004673 fluoride salts Chemical class 0.000 description 5
- 229910052732 germanium Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- TWFZGCMQGLPBSX-UHFFFAOYSA-N carbendazim Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 150000004060 quinone imines Chemical class 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- RHYBFKMFHLPQPH-UHFFFAOYSA-N N-methylhydantoin Chemical compound CN1CC(=O)NC1=O RHYBFKMFHLPQPH-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229960000458 allantoin Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical class [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- RFTORHYUCZJHDO-UHFFFAOYSA-N 1,3-dimethylimidazolidine-2,4-dione Chemical compound CN1CC(=O)N(C)C1=O RFTORHYUCZJHDO-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- XGJPUQFWFRCCFO-UHFFFAOYSA-N 3,3,4,4-tetramethylpyrrolidine-2,5-dione Chemical compound CC1(C)C(=O)NC(=O)C1(C)C XGJPUQFWFRCCFO-UHFFFAOYSA-N 0.000 description 1
- BHYLCQRRNWUVHE-UHFFFAOYSA-N 3-ethylpyrrolidine-2,5-dione Chemical compound CCC1CC(=O)NC1=O BHYLCQRRNWUVHE-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006013 carbendazim Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000007979 citrate buffer Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- HAPOVYFOVVWLRS-UHFFFAOYSA-N ethosuximide Chemical compound CCC1(C)CC(=O)NC1=O HAPOVYFOVVWLRS-UHFFFAOYSA-N 0.000 description 1
- 229960002767 ethosuximide Drugs 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005111 flow chemistry technique Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- VDDXNVZUVZULMR-UHFFFAOYSA-N germanium tellurium Chemical compound [Ge].[Te] VDDXNVZUVZULMR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- BZWNJUCOSVQYLV-UHFFFAOYSA-H trifluoroalumane Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Al+3].[Al+3] BZWNJUCOSVQYLV-UHFFFAOYSA-H 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/011—Electroplating using electromagnetic wave irradiation
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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- 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
-
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- 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
- C25D7/126—Semiconductors first coated with a seed layer or a conductive layer for solar cells
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
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- 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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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- 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
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Description
本發明係關於一種於半導體上鍍覆銅之方法。更具體而言,本發明係關於使用一價銅浴於半導體上鍍覆銅之方法。
經摻雜之半導體(如光伏裝置及太陽能電池)之金屬鍍覆係包括於該等半導體之正面及背面上形成導電接觸(contact)。該金屬塗層必須能與該半導體構建歐姆接觸,從而保證電荷載劑擺脫該半導體並進入該等導電接觸中而無干擾。為了避免電流損耗,經金屬化之接觸網格必須具有充足之電流傳導性,亦即,高導電性或足夠高之導體軌道橫截面。
對於太陽能電池背面之金屬塗層,存在大量符合上揭需求之製程。舉例而言,為了提升太陽能電池背面之電流傳導,係增強該背面下方之直接p-摻雜。鋁係往往用於此目的。該鋁係,舉例而言,藉由蒸汽沉積或藉由印刷於該背面上並分別受驅進入或成合金進入而予欲以施用。當金屬塗佈於該正面或光入射面時,目標係達成最小量之該主動半導體表面之屏蔽,從而施用盡可能多之該表面來捕獲光子。
使用厚膜技術之金屬塗佈係用於金屬化導體軌道之傳統方法。所使用之糊狀物係包括金屬粒子,且作為結果,其係導電。該等糊狀物係藉由篩網、罩、墊印刷(pad
printing)或糊狀寫入(paste writing)予以施用。一般使用之製程係篩網印刷製程,其中,作成具有80微米(μm)至100μm之最小線寬的指狀金屬線。即便具有此網格寬度,導電性損耗係較純金屬結構明顯。這可能對串聯電阻及太陽能電池之填充因子及效能具有負面影響。此影響係於較小之印刷式(print-on)導體軌道寬度中被放大,蓋因該製程造成該等導體軌道變得更平。界於該等金屬粒子之間之非導電性氧化物及玻璃組分構成此導電性下降之根本原因。
用於製造該等正面接觸之更複雜之製程係使用雷射或光微影技術來界定該等導體軌道結構。導體軌道係隨之被金屬化。通常,為了全力達成導電性所需之足量之黏合強度及所欲之厚度,往往使用多種金屬塗佈步驟以施用該金屬塗層。舉例而言,當使用濕化學金屬塗佈製程時,係藉由鈀催化劑之手段將第一精細金屬塗層沉積於該電流軌道上。這往往以鎳之無電沉積予以加強。為了增加傳導性,可藉由無電沉積或電解沉積將銅沉積於該鎳上。隨後,可將錫或銀之精細層塗覆於該銅上以保護其不被氧化。
經摻雜之半導體晶圓之銅鍍覆的一個問題為,業經發現該銅使得n-型摻雜及p-型摻雜之半導體晶圓劣化,因此縮短其壽命。銅污染與晶圓摻雜之間之協同效應業經被披露。與其他金屬如鐵相比,對壽命產生激烈減少所需之銅的量相對較高,且相對可接受壽命仍可於中度污染之矽發現。舉例而言,當銅濃度為3×1014
cm-3
時,1歐姆公分(Ω cm)
之p-型矽的壽命接近10微秒(μs),其係與160μm之擴散長度一致。較高量之銅甚至進一步縮短壽命,且當濃度為3×1015
cm-3
時,發現這一趨勢仍未達到飽和。此外,值得注意的是,依據晶圓之電阻,特定之銅濃度可達成之壽命差異極大,而較低之電阻對應較短之壽命。銅劑量及摻雜劑濃度兩者對於壽命皆具有強烈影響之事實,對於未來研究矽中以及光伏裝置製造用銅鍍覆浴之發展中的銅很重要。這一問題於J.Bartsch等人於《電化學會志(Journal of The Electrochemical Society,157(10)H942-H946(2010))》發表之文章“銅金屬化對矽太陽能電池之長期衝擊之快速測定(Quick Determination of Copper-Metallization Long-Term Impact on Silicon Solar Cells)”中有詳細揭示。
經摻雜之半導體晶圓之銅鍍覆的另一問題為,銅於背面之含鋁電極及銀匯流排上之非所欲之沉積,危害該等晶圓之效能。當該浴中之銅離子為二價銅離子或Cu2+
離子時,出現此非所欲之銅鍍覆。該銅鍍覆浴典型係酸性。不施以外加電流時,沿著該電池之背面形成不同之金屬,係藉由此金屬差異性所產生之浸潤製程而出現該銅沉積。又,沉積於該背面之銅可能遷移進入半導體並損害該半導體。此外,此含有二價銅離子之銅鍍覆浴並不澄清,其色澤暗沉,因此於光引發之鍍覆製程中阻礙光到達該半導體。這可能造成非均勻之銅鍍覆,導致經鍍覆之銅的厚度沿電流軌道而改變,且可能危害鍍覆速率,並因此降低該
鍍覆製程之效率。據此,需要一改善之於半導體晶圓上鍍覆銅之方法,以形成正面電流軌道。
提供一種方法,係包括提供半導體,該半導體係包括正面、背面及PN接面,該正面係包括導電軌道之圖案,該導電軌道之圖案係包含下方層,且該背面係包括金屬接觸;將該半導體與一價銅鍍覆組成物接觸,以及將銅鍍覆於該導電軌道之下方層上。
該方法能將銅沉積於該半導體正面之導電軌道之下方層上,且背面之金屬接觸上實質無銅沉積。此外,與包括二價銅離子之更暗之藍綠色銅鍍覆浴相比,該一價銅鍍覆組成物係澄清者,因此,於光誘發之銅鍍覆過程中,光輕易地穿行透過該鍍覆組成物到達該半導體。這增加了該半導體上之光強度,並改善該電流軌道之下方層上之銅沉積物之均勻性。通常,於相當之電流密度下,該一價銅鍍覆組成物沉積銅之鍍覆速率比包括二價銅離子之銅鍍覆浴更快,且於相同時間內提供與後者相當之銅沉積厚度及電流軌道寬度。與包括二價銅離子之銅鍍覆浴相比,其整體鍍覆效率及銅鍍覆效能得以改善。再者,該方法能以銅替代更昂貴之銀,其中,銀係典型用於塗佈電流軌道之下方層。
如貫穿本說明書所使用者,術語「沉積」與「鍍覆」可互換地使用。術語「電流軌道」與「導電軌道」可互換
地使用。術語「組成物」與「浴」可互換地使用。非特定冠詞「一(a)」及「一(an)」係欲以包括單數及複數兩者。術語「選擇性沉積」係意指金屬沉積係出現於基板上所欲之具體區域。術語「一價銅離子」為Cu+,而術語「二價銅離子」為Cu2+
。術語「lux=lx」係照明之單位,其等於1流明/平方公尺(m2
);以及,1 lux=1.46毫瓦之頻率為540太赫茲(tetrahertz)之輻射電磁(EM)功率。
除了文中另行特別指出者之外,下列縮寫係具有下列意義:℃=攝氏度;g=公克;mg=毫克;mL=毫升;L=公升;A=安培;dm=公寸;ASD=A/dm2
;cm=公分;μm=微米;nm=奈米;LIP=光誘發之鍍覆或光輔助之鍍覆;V=伏特;UV=紫外線;以及IR=紅外線。
除了特別另行指出者外,全部百分比及比例係基於重量計。全部範圍係包括邊值且可以任何次序組合,除非此等數值範圍之和明顯應受限於加總最高為100%。
方法係包括提供半導體,該半導體係包括正面、背面及PN接面,該正面係包括導電軌道之圖案,該導電軌道之圖案係包含下方層,且該背面係包括金屬接觸;將該半導體與一價銅鍍覆組成物接觸,以及將銅鍍覆於該導電軌道之下方層上。
可使用一價銅鍍覆組成物將銅以各種厚度範圍沉積於該電流軌道之下方層上。該一價銅鍍覆組成物可係不含氰化物。可使用該一價銅組成物於該電流軌道中形成多層,其中,該銅層係夾置於一層或多層導電下方層與一層
或多層導電頂層之間;或可使用該一價銅組成物形成積層(build-up layers)以完成該電流軌道。較佳係使用該等一價銅組成物於該下方層上沉積一層薄膜層,其係導電金屬或金屬矽化物種子層、阻擋層或其組合。
可採用可溶於該鍍覆組成物中之一價及二價銅化合物之形式提供一種或多種銅離子源。該鍍覆組成物中可包括一種或多種還原劑以將該二價銅離子(Cu2+
)還原為一價銅離子(Cu+
)並將一價銅離子維持於一價狀態。可包括於該一價銅鍍覆組成物中之銅化合物係包括,但不限於,氟硼酸銅、草酸銅、氯化亞銅、氯化銅、硫酸銅、氧化銅及甲磺酸銅。儘管可包括氯化亞銅及氯化銅作為一價銅離子源,較佳之銅化合物係氧化銅、硫酸銅、甲磺酸銅及其他傳統水溶性非鹵銅鹽。該等銅化合物典型係硫酸銅及甲磺酸銅。該一價銅組成物中可包括一種或多種銅化合物,其量為1 g/L至40 g/L,或諸如自5 g/L至30 g/L。
可包括於該鍍覆組成物中之還原劑係包括,但不限於,鹼金屬亞硫酸鹽類、鹼金屬亞硫酸氫鹽類、羥胺類、肼類、硼烷類、糖類、乙內醯脲及乙內醯脲衍生物、甲醛及甲醛類似物。該等還原劑係以10 g/L至150 g/L,或諸如自15 g/L至60 g/L之量包括於該鍍覆組成物中。
錯合劑亦可包括於該一價銅鍍覆組成物中。該錯合劑係包括,但不限於,醯亞胺及醯亞胺衍生物以及乙內醯脲及乙內醯脲衍生物。醯亞胺衍生物係包括,但不限於,琥珀醯亞胺、3-甲基-3-乙基琥珀醯亞胺、1-3甲基琥珀醯亞
胺、3-乙基琥珀醯亞胺、3,3,4,4-四甲基琥珀醯亞胺、3,3,4-三甲基琥珀醯亞胺及馬來醯亞胺。乙內醯脲衍生物係包括,但不限於,1-甲基乙內醯脲、1,3-二甲基乙內醯脲、5,5-二甲基乙內醯脲及尿囊素(allantoin)。該鍍覆組成物中包括之錯合劑之量係取決於該組成物中銅的量。銅與錯合劑之莫耳比典型係自1:1至1:5,或諸如自1:2至1:4。錯合劑濃度之典型範圍係自4 g/L至300 g/L,或諸如自10 g/L至100 g/L。
該一價銅鍍覆組成物之pH範圍係自7至12,或諸如自7至10,或諸如自8至9。可使用與該鍍覆組成物相容之任何之鹼或鹼金屬鹽來調節pH。此等鹼係包括,但不限於,氫氧化鈉、氫氧化鉀、氫氧化銨及碳酸鈉。
該鍍覆組成物可視需要包括一種或多種銅鍍覆浴用之傳統浴添加劑如一種或多種導電鹽類,以及一種或多種提升該銅沉積物之均勻性及亮度的添加劑。可加入導電鹽類以改善該鍍覆組成物之導電性。可使用可溶於該鍍覆組成物中並與該鍍覆組成物相容之任何鹽。此等導電鹽類係包括,但不限於,硫酸鹽類、磷酸鹽類、檸檬酸鹽類、葡萄糖酸鹽類及酒石酸鹽類之一者或多者。此等鹽之實例係硫酸鈉、焦磷酸鉀、磷酸鈉、檸檬酸鈉、葡萄糖酸鈉及羅謝耳(Rochelle)鹽如酒石酸鉀鈉。可以包括之此等鹽的量係5 g/L至75 g/L,或諸如自10 g/l至50 g/L。較佳係該銅鍍覆組成物不包括氯化物及其他鹵化物。
該鍍覆組成物中可包括提升經鍍覆之銅之均勻性及
亮度的添加劑。此等添加劑可包括,但不限於,有機胺化合物如三伸乙四胺及四伸乙五胺,以及氧烷基多胺類如聚氧丙基-三胺。所使用之胺的量係取決於其於該組成物中之活性,亦即,其增亮該沉積物之能力。舉例而言,典型係以佔鍍覆組成物0.05 mL/L之濃度使用三伸乙四胺,而聚氧丙基三胺之濃度可為0.1 g/L。因此,這添加劑之量可係自0.01 mL/L至0.5 mL/L之範圍。
典型之一價銅鍍覆組成物可藉由下述製備之:首先,將錯合劑溶解於水中,隨後加入結晶形式或呈漿料之銅離子源。隨後攪拌該水溶液以溶解該銅化合物,調節pH,再加入一種或多種還原劑。隨後將其他添加劑加入該鍍覆組成物中。可以於寬廣溫度範圍製備該鍍覆組成物。典型係於室溫製備。於銅鍍覆過程中,該一價銅鍍覆組成物之溫度可自15℃至70℃之範圍,或諸如自40℃至50℃。
該等半導體可係由單晶矽或多晶矽或非晶形矽組成。雖然下述說明係關於矽半導體晶圓,亦可使用其他適宜之半導體晶圓,如砷化鎵、矽-鍺、及鍺。此等半導體典型係用於光伏裝置及太陽能電池之製造中。當使用矽晶圓時,他們典型係具有p-型基極摻雜(base doping)。
該等半導體晶圓可係圓狀、方形或矩形之形狀或可係任何之其他適宜之形狀。此等晶圓可具有寬範圍之尺寸及表面電阻。舉例而言,圓狀晶圓可具有150毫米(mm)、200 mm、300 mm、400 mm或更大之直徑。
將晶圓之背面金屬化以提供低電阻晶圓。可使用任何
之傳統方法。典型地,該半導體晶圓之表面電阻,亦稱為薄片電阻,係40至90歐姆(ohm)/平方單位(square),或諸如自40歐姆/平方單位至60歐姆/平方單位,或諸如自60歐姆/平方單位至80歐姆/平方單位。
整個背面可塗覆有金屬,或部份該背面可塗覆有金屬以形成諸如網格。匯流排典型係包括於該晶圓之背面上。可藉由各種技術提供該背面金屬化。於一態樣中,係以導電膠之形式如含銀糊、含鋁糊或含銀鋁糊之形式將金屬塗層施用至該背面;但是,亦可使用包括金屬如鎳、鈀、銅、鋅或錫之其他糊。此等導電糊典型係包括包埋於玻璃基質中之導電粒子,以及有機黏合劑。可藉由多種技術如篩網印刷將導電糊施用至晶圓。施用該糊之後,將其燒製(fired)以移除該有機黏合劑。當使用含鋁之導電糊時,鋁部份地擴散進入該晶圓之背面中;或者,若所使用之糊中亦含有銀,則可與銀形成合金。該含鋁糊之使用可改善電阻接觸並提供「p+」-摻雜區域。亦可藉由前述鋁或硼之施用以及後續之相互擴散而產生重度摻雜之「p+」-型區域。於一態樣中,可於施用該背面金屬塗層之前,將含鋁糊施用至該背面並燒製。可視需要於施用該背面金屬塗層之前移除來自經燒製之含鋁糊之殘質。於另一態樣中,可將種子層沉積於該晶圓之背面上,且可藉由無電鍍覆或電解電鍍將金屬塗層沉積於該種子層上。
為了賦予該晶圓之正面表面會降低反射之改善之光入射幾何學,可對該表面進行晶體定向紋理(crystal-
oriented texture)蝕刻如形成稜錐(pyramid)。為了產生半導體接面,磷擴散或離子植入發生於該晶圓之正面以產生n-摻雜(n+或n++)之區域並對該晶圓提供PN接面。該n-摻雜之區域可指代為射極(emitter)層。
將抗反射層加至該晶圓之正面或射極層上。此外,該抗反射層可作為鈍化層。適宜之抗反射層係包括,而不限於,氧化矽層如SiOx
、氮化矽層如Si3
N4
、氧化矽層及氮化矽層之組合、以及氧化矽層、氮化矽層與氧化鈦層如TiOx
之組合。於前述式中,x係氧原子之數目。可藉由多種技術如藉由各種氣相沉積方法,舉例而言,化學氣相沉積及物理氣相沉積,沉積此等抗反射層。亦可於金屬化之前預先進行化學邊緣隔離步驟以確保不存在自射極體至背面之電流軌道。可使用該技藝中習知之傳統蝕刻溶液完全邊緣隔離。
將晶圓之正面金屬化以形成電流軌道與匯流排之金屬化圖案。該等電流軌道典型係垂直於匯流排,且與該等匯流排相比,該等電流軌道典型係具有相對精細(亦即,尺寸)之結構。
可使用含有銀之金屬糊形成電流軌道。該銀糊係選擇性地施用至該抗反射層如氮化矽之表面,達所欲厚度,此係取決於最終之所欲電流軌道的厚度。其量可變,且該量係彼等熟識該技藝之人士所熟知者。該糊除了包括銀之外,亦可包括有機黏合劑及玻璃基質,其中,導電粒子係包埋於該玻璃基質中。此等糊係該技藝中習知者並可商購之。
具體之配方變化係取決於製造商,因此該糊之配方通常係專屬者。可藉由傳統之於半導體上形成電流軌道中所使用的方法施用該糊。此等方法係包括,但不限於,篩網印刷、模板印刷、拓印(dabber printing)、糊刻(paste inscription)及輥壓。該等糊係具有適用於此等施用方法之黏度。
將塗有糊之半導體置於燒結爐中以燒穿該抗反射層,使得該糊於該糊之金屬與該半導體之正面或射極層之間形成半熔質(frit)或接觸。可使用傳統燒結方法。依據具體之糊組成物,該燒結可於氧化性氣氛或具有最小氧含量之惰性氣體中進行。亦可進行兩段燒製製程:先於低氧下於高達400℃之溫度燒製,隨之於惰性氣體或還原性氣氛下於較高溫度燒製。糊燒製典型係於標準大氣壓下完成。此等方法係該技藝中習知者。
於另一方法中,該晶圓之正面或射極層係塗有抗反射層如氮化矽。隨後,將開口或圖案界定於該正面上。該圖案穿抵該抗反射層並暴露出該晶圓之半導體本體的表面。可使用各種製程以形成該圖案,該各種製程係全部為該技藝中習知者如,但不限於,雷射剝蝕、機械手段及光微影製程。該機械手段係包括鋸切及刮擦。圖案寬度可係自10μm至90μm之範圍。
該開口可視需要與酸(如氫氟酸)或鹼接觸以紋理化或粗糙化曝露之該半導體之射極層的表面。亦可使用電化學蝕刻製程以粗糙化該射極層之表面。各種電化學蝕刻製
程係該技藝中習知者。此等方法之一係包括使用氟化物與酸式氟化物之溶液以於該射極層之表面上形成奈米孔層的陽極蝕刻製程。
於一方法中,係使用陽極蝕刻製程以粗糙化該射極層。可使用傳統氧化劑以再生原有之氧化物。典型係使用1至3wt%過氧化氫水溶液完成氧化。其他氧化劑係包括,但不限於,次氯酸鹽、過硫酸鹽、過氧有機酸及高錳酸鹽之水溶液。當該半導體晶圓係單晶時,該氧化性溶液典型係pH大於7,或諸如自8至12之鹼性溶液。當該半導體晶圓係由矽製成時,係於曝露之截面上形成SiOx
層。典型係將該半導體晶圓浸潤於含有該氧化性溶液之流動製程腔中或經過該腔處理。亦可藉由將該半導體晶圓曝露於大氣環境中而自發地出現氧化。
隨後,以包括一種或多種酸式氟化物源、一種或多種氟化物鹽或其混合物之組成物蝕刻該半導體晶圓之電流軌道的射極層,以於經氧化之表面上形成奈米孔層。酸式氟化物源化合物係包括,但不限於,鹼金屬酸式氟化物如酸式氟化鈉及酸式氟化鉀、氟化銨、酸式氟化銨、氟硼酸鹽、氟硼酸、酸式氟化錫、酸式氟化銻、四氟硼酸四丁基銨、六氟化鋁、以及脂肪胺、芳香胺及含氮雜環化合物之四級銨。氟化物鹽係包括,但不限於,鹼金屬氟化物,如氟化鈉及氟化鉀。包括於該組成物中之酸式氟化物源化合物及氟化物鹽的量典型係5 g/L至100 g/L,或諸如自10 g/L至70 g/L,或諸如自20 g/L至50 g/L。
可包括於該組成物中之酸係包括,但不限於,胺磺酸;烷磺酸如甲磺酸、乙磺酸及丙磺酸;烷醇磺酸;芳基磺酸如甲苯磺酸、苯磺酸及酚磺酸;含胺基之磺酸如醯胺基磺酸(amido sulfonic acid);無機酸如硫酸、硝酸及鹽酸;胺基酸;羧酸,包括單羧酸、二羧酸及三羧酸;及其酯、醯胺及任何未反應之酸酐。再者,該組成物可含有酸之混合物。當該組成物中包括兩種或更多種羧酸時,至少一者係含有酸性質子以形成酸式氟化物。此等酸通常可自各種來源如阿德瑞希化學公司(Aldrich Chemical Company)商購之。通常,該電化學組成物中包括之酸及酸酐的量係1 g/L至300 g/L,或諸如自10 g/L至200 g/L,或諸如30 g/L至100 g/L。
藉由將化學計量學量之一種或多種酸與一種或多種酸式氟化物源化合物或一種或多種氟化物鹽或其混合物組合來製備電化學組成物。進行混合直至該酸式氟化物組分或氟化物鹽係溶解於該酸中。可加入水進一步混合以溶解任何未溶解之組分。
或者,可將一種或多種酸酐加入至少一種酸式氟化物源之水溶液中,以一旦與水接觸即形成至少一種羧酸。該水性酸式氟化物源化合物中可存在一種或多種羧酸,但須滿足係以化學計量學採用足量之酸酐以獲得1至5wt%之含水量。隨後混合這一組合,直至該酸酐水解且該酸式氟化物源化合物溶解。可額外加入水進一步混合,直至全部組分溶解。
該電化學組成物典型係包括鹼金屬酸式氟化物、氟化銨及酸式氟化銨之一者或多者作為該酸式氟化物源化合物。該酸式氟化物源化合物更典型係鹼金屬酸式氟化物,如酸式氟化鈉及酸式氟化鉀。當該酸式氟化物源化合物係鹼金屬酸式氟化物時,該電化學組成物中係包括一種或多種無機酸如胺磺酸。當該酸式氟化物源化合物係酸式氟化銨或氟化銨時,該電化學組成物中係包括一種或多種羧酸。典型係包括單羧酸如乙酸。
廣泛各種界面活性劑可視需要用於該電化學組成物中。可使用任何之陰離子性、陽離子性、兩性及非離子性界面活性劑,只要其不干擾蝕刻之效能即可。所包括之界面活性劑之量可為傳統之量。
該電化學組成物視需要含有一種或多種額外之組分。此等額外之組分係包括,而不限於,光亮劑、粒子細化劑及延性增強劑。此等額外之組分係該技藝中習知者且可以傳統之量使用之。
該電化學組成物視需要含有緩衝劑。緩衝劑係包括,但不限於,硼酸鹽緩衝劑(如硼砂)、磷酸鹽緩衝劑、檸檬酸鹽緩衝劑、碳酸鹽緩衝劑及氫氧化物緩衝劑。所使用之緩衝劑的量係足以將該電化學組成物之pH維持於1至6,典型自1至2之所欲水準。
該半導體晶圓係浸沒於容置於化學惰性蝕刻及鍍覆槽中之電化學組成物中。該電化學組成物之工作溫度可係自10至100℃,或諸如自20至50℃。將背側電位(整流器)
施用至該半導體晶圓。惰性相對電極亦浸沒於該槽中。該相對電極係鉑線或篩網電極。該槽、半導體晶圓、電化學組成物及整流器係彼此電性連通。
陽極電位係於該電化學組成物中及該半導體晶圓處產生並維持預設之時間,之後將電流切斷預設之時間,並將該循環重複足夠次數,以於經氧化之射極層上提供實質均勻之奈米孔層並同時滲透經氧化之射極層的表面,因此不破壞該半導體之電效能。該方法係界於滲透射極層以形成實質均勻之奈米孔射極層表面與薄片電阻之間的平衡,其使得能夠沉積金屬,造成金屬層與該半導體晶圓之間之良好黏附及歐姆接觸。此外,該方法係界於最小化對於該射極層上之抗反射特此之攻擊或損害與同時形成奈米孔射極層之間的平衡。該射極層之經氧化之部份係作成奈米孔達一定深度,因此金屬良好地黏附至該射極層,且同時,該射極層之電阻係足夠導電以至於能鍍覆金屬。該奈米孔層滲透進入該射極層越深,該射極之薄片電阻越大。通常,該實質均勻之奈米孔層滲透進入該射極層之深度足夠深,而使得相對於開始施用該陽極電位之前射極層之薄片電阻,該射極層之薄片電阻增加5%至40%,或諸如自20%至30%。該均勻奈米孔射極層之薄片電阻係200歐姆/平方單位或更低。諸如射極層厚度及摻雜輪廓之因素亦為決定射極層奈米孔深度及射極層電阻時應予以考慮的參數。可進行少量實驗以決定該射極層奈米孔深度及射極層電阻,以對於特定之半導體晶圓達成金屬鍍覆及良好之金屬黏附。
通常,施用該陽極電位過程中的電流密度可係自0.01 A/dm2
至2 A/dm2
之範圍,或諸如自0.05 A/dm2
至1 A/dm2
。然而,可進行少量實驗以決定對於特定之半導體晶圓的較佳之電流密度設定、施用及切斷該陽極電位之時間段。該等參數係取決於該半導體晶圓之厚度以及該射極層之起始厚度及該奈米孔射極層之所欲厚度。若該射極層之奈米孔部份太深,可能損害半導體並進而增加其薄片電阻。太高之薄片電阻破壞形成於該射極層之奈米孔部份上之電流軌道的導電性。此外,該射極層表面上之非均勻之奈米孔層可能造成後續之鍍覆金屬層的黏附性差。陽極電位典型係施用0.5秒或更長時間,或諸如0.5秒至2秒,或諸如自3秒至8秒。於該循環中,該陽極電位中斷之時間可係1秒及更長之範圍,或諸如自3秒至10秒,或諸如10秒至50秒。該循環之次數可係自5至80之範圍,或諸如自10至100。
又,於金屬鍍覆之前,可遮蔽該半導體之邊緣。邊緣遮蔽降低金屬化過程中該半導體晶圓由於n-型射極層與p-型射極層之金屬沉積物的橋接所造成之半導體晶圓分流(shunting)的可能性。可藉由在金屬化之前,沿著該半導體晶圓之邊緣施用傳統之鍍覆阻劑而進行邊緣遮蔽。此等鍍覆阻劑可係蠟系組成物,其係包括一種或多種蠟如,褐煤蠟、石蠟、大豆蠟、植物蠟及動物蠟。此外,此等阻劑可包括一種或多種交聯劑如,傳統之丙烯酸酯、二丙烯酸酯及三丙烯酸酯,以及一種或多種用於在曝光至照射如UV
及可見光時固化該阻劑之固化劑。固化劑係包括,但不限於,傳統之用於光阻劑劑其他光敏組成物中之光起始劑。此等光起始劑係該技藝中習知者且業經公開發表於文獻中。可藉由傳統之篩網印刷過程或藉由選擇性噴墨製程施用此等鍍覆阻劑。或者,可使用抗反射層對該半導體晶圓進行邊緣遮蔽。這可以在形成該抗反射層之過程中,藉由將用以作成該抗反射層之材質沉積於該半導體層之邊緣上而完成。
無論該電流軌道係藉由金屬糊方法或藉由一種或多種上揭之選擇性紋理化及粗糙化方法予以形成者,隨後,將作為種子層、阻擋層或其組合之金屬或金屬矽化物之下方層沉積於經燒製之金屬糊上或沉積於經紋理化及粗糙化之射極層上。可使用多種金屬以形成該下方層。該等金屬典型係鎳、鈀、銀、鈷及鉬。亦可使用此等金屬之各種合金。該等金屬典型係鎳、鈀或鈷。該金屬更典型係鎳或鈀。該金屬最典型係鎳。可藉由使用該技藝中習知之傳統之無電鍍覆、電解電鍍、LIP、濺射、化學氣相沉積及物理氣相沉積方法沉積此等下方層。儘管各種金屬係預見能形成該下方層,下揭之方法係使用鎳作為該金屬;然而,於該等使用傳統之無電及電解金屬鍍覆浴之方法中,諸如鈀、銀及鈷之金屬可輕易地替代鎳。
典型係藉由光誘發鍍覆來沉積鎳。若該鎳源係無電鎳組成物,不施用外加電流即完成鍍覆。若該鎳源係來自電解鎳組成物,係將背側電位(整流器)施用至該半導體晶圓
基板。典型之電流密度係自0.1 A/dm2
至2 A/dm2
,更典型係自0.5 A/dm2
至1.5 A/dm2
。該光可係連續光或脈衝光。可用以鍍覆之光係包括,但不限於,可見光、紅外線、UV及X-射線。光源係包括,但不限於,白熾燈、LED光(發光二極體)、紅外燈、螢光燈、鹵燈及雷射。光強可係自400 lx至20,000 lx之範圍,或諸如自500 lx至7500 lx。進行鎳鍍覆,直至厚度為20nm至1μm厚,或諸如自50nm至150nm厚之下方層完成沉積;然而,確切之厚度係取決於各種因子,諸如半導體尺寸、電流軌道圖案及該半導體之幾何形狀。可進行少量實驗以測定對於給定半導體之確切鎳層厚度。
於另一具體實施態樣中,上揭之電化學組成物中可包括鎳。於蝕刻該射極層以形成多孔表面之後,該電流係自陽極電流變為陰極電流,以沉積該下方層。用於此下方層形成之電流密度係與上揭者相同。可將光施用至該晶圓之正面以進行光誘發鍍覆。
可使用傳統之無電及電解鎳浴以形成該下方層。可商購之無電鎳浴之實例係包括DurapositTM
SMT 88、NiPositTM
PM 980及PM 988。全部可自羅門哈斯電子材料公司(Rohm and Haas Electronic Materials,LLC,Marlborough,MA,U.S.A)購得。可商購之電解鎳浴之實例係可自羅門哈斯電子材料公司獲得之Nickel GleamTM
系列之電解產品。適宜之電解鎳鍍覆浴之其他實例係於第3,041,255號美國專利中揭露之瓦特型(Watts-type)浴。
於另一形成該鎳下方層之具體實施態樣中,係將光以初始強度施用至該半導體直至預設之時間,之後,於剩餘之鍍覆循環中,將該初始光強降至預設之量,以將鎳沉積於該經摻雜之半導體的電流軌道上。於初始光強之後施用至該半導體以及施用至剩餘之鍍覆循環的光強往往係小於該初始光強。該初始光強以及於初始階段之後之降低之光強的絕對值係有變動,且他們可於該鍍覆製程中變動以達成最優之鍍覆結果,只要該初始光強高於剩餘之鍍覆循環所用之光強即可。若該初始光強於該初始時間段中變動,施用至剩餘之鍍覆循環的光強可為基於該初始光強之平均值。可預先進行少量實驗以決定適宜之初始光強、適宜之用於施用該初始光強之時間段、以及施用至剩餘之鍍覆循環之光強。若該初始光強保持過久,則由於相對高之鎳沉積張力(stress),可能出現極差之鎳沉積黏附並剝落。若該光被衰減,則可能於該半導體晶圓之背面上出現非所欲之鎳鍍覆。
通常,用於施用該初始光強之時間段係大於0秒至15秒。典型地,該初始光強係施用至該半導體0.25秒至15秒,更典型係2秒至15秒,最典型係5秒至10秒。
通常,該經降低之光強係該初始光強之5%至50%。典型地,該經降低之光強係該初始光強之20%至50%,或諸如自30%至40%。
通常,初始施用至該半導體之光的量可係8000 lx至20,000 lx,或諸如自10000 lx至15,000 lx。通常,於
剩餘之鍍覆循環中施用至該半導體晶圓之光的量可係自400 lx至10,000 lx,或諸如自500 lx至7500 lx。
於又一具體實施態樣中,於沉積鎳之後,將該晶圓燒結以形成矽化物。典型地,於燒結過程中,並非全部之鎳沉積物皆與該半導體材質反應。據此,仍有一層鎳層保留於該矽化鎳之頂部。該矽化鎳係處於該鎳層與相鄰之半導體材質之間。燒結係基於燈之爐(IR)內進行,其係達成300℃至600℃之晶圓溫度峰值。所使用之燒結溫度越高,該半導體保留於該爐中之燒結循環或時間段越短。若該半導體於給定溫度於爐中停留過久,鎳可能擴算進入該晶圓過深而滲透該射極層,從而分流該電池。此等燒結製程係該技藝中習知者,且可能需要少量實驗以達成最優之燒結循環。視需要,於形成該矽化鎳之後,可使用無機酸如硝酸將未反應之鎳自該矽化鎳剝離。
形成該下方層之後,自一價銅浴於其上鍍覆銅層。沉積於該下方層上之銅層的厚度可係1μm至50μm之範圍,或諸如自5μm至25μm。可藉由電解電鍍或藉由LIP完成銅鍍覆。當藉由電鍍完成鍍覆時,典型係正面接觸鍍覆,而LIP典型係藉由背側接觸鍍覆完成。銅鍍覆過程中之電流密度可係0.01 A/dm2
至5 A/dm2
之範圍,或諸如自0.5 A/dm2
至2 A/dm2
。當使用LIP以鍍覆銅時,光係施用至該晶圓之正面,且背側電位(整流器)係施用至該半導體晶圓基板。藉由以光能照射該半導體晶圓之正面,鍍覆出現於該正面。入射之光能於該半導體中產生電流。該光可係連
續光或脈衝光。舉例而言,可藉由以機械段路器中斷該光而達成脈衝照射,或可使用電子裝置以將光之電源基於所欲之循環間歇地循環。可用以鍍覆之光係如上揭者。通常,鍍覆過程中施用至該半導體晶圓之光的量可係10,000 lx至70,000 lx,或諸如自30,000 lx至50,000 lx。
典型地,錫飾層係隨後沉積於該銅上,以防止該銅層之氧化。錫飾層之厚度可係0.25μm至2μm之範圍。可使用傳統之錫鍍覆浴於該銅上沉積該飾層。可藉由包括光誘發鍍覆之傳統無電及電解方法完成錫鍍覆。當使用電解錫浴時,電流密度可係自0.1 A/dm2
至3 A/dm2
之範圍。作為錫之替代,可鍍覆錫/鉛合金之飾層。除了錫或錫/鉛之外,可鍍覆銀或無電鎳浸沒金層。又,可將有機可溶性防腐劑施用至該銅層或錫或錫/鉛飾層。此等有機可溶性防腐劑係該技藝中習知者。
該等方法可將銅沉積於該半導體之正面的導電軌道圖案上,而該背面之金屬接觸上實質無銅沉積。該背面金屬接觸上之銅典型係導致非所欲之銅擴散進入本體矽中。銅本質上係該半導體晶圓之毒藥,且較佳係限制其於光伏裝置之製造中的使用,但同時,銅亦為製造光伏裝置的重要金屬。此外,與包括二價銅離子之較暗之藍綠色銅鍍覆浴相比,該一價銅鍍覆組成物係澄清,因此,於光誘發之銅鍍覆過程中,光輕易地穿行透過該鍍覆組成物至該半導體。這增加該半導體上之光強,並改善該電流軌道上銅沉積物的均勻性。通常,與包括二價銅離子之銅鍍覆浴相比,
於相當之電流密度下,該一價銅鍍覆組成物沉積銅之鍍覆速率更快,後者同時提供與前者相當之銅沉積厚度及電流軌道寬度。整體鍍覆效率及銅鍍覆效能較包括二價銅離子之銅鍍覆浴有所改善。再者,該方法能以銅替代更昂貴之銀(銀典型係用於形成電流軌道)。
下述實施例係用以詳細說明本發明,而非欲以限制本發明之範疇。
提供六片正面含有複數個銀糊產生之電流軌道及匯流排的單晶半導體晶圓。每一晶圓之背側係包括鋁電極。將該等晶圓摻雜以提供PN接面。隨後將每一晶圓於Ohaus EO2140分析天平上稱重。記錄每一晶圓之重量並顯示於下表II中。
隨後,將三片晶圓浸沒於單獨之含有ENLIGHTTM
420電解銅鍍覆浴(自羅門哈斯電子材料公司購得)的化學惰性鍍覆槽中。該等浴係包括為二價銅離子(Cu2+
)之銅離子,且具有低於1之pH。該等浴係不含銅離子還原劑。該等浴係深藍色。相對電極係可溶性之經磷化之銅陽極。每一晶圓之背面及相對電極係連結至三個分離之整流器,以於該等浴與該等晶圓及相對電極之間提供電性連通。該等浴之溫度係維持於30℃,且來自250瓦鹵燈之光係施用至每一晶圓之正面。對每一浴施以0.34伏特之電壓。第一浴中所施用之電流密度係2 A/dm2
,第二浴中之電流密度係2.3
A/dm2
,且第三浴中之電流密度係2.5 A/dm2
。施行LIP 7.5分鐘以將銅層沉積於每一晶圓之電流軌道上。將各晶圓自個自之鍍覆槽中移除,以水沖洗,並隨後於室溫空氣乾燥。隨後,將每一晶圓於Ohaus EO2140分析天平上稱重。重量係記錄於下表II中。
隨後,將第二組三片晶圓浸沒於分離之含有下表1中揭露之一價銅浴的化學惰性鍍覆槽中。
相對電極係可溶性經磷化之銅陽極。每一晶圓之背面及相對電極係連結至三個分離之傳統整流器,以於該等浴與該等晶圓及相對電極之間提供電性連通。該等浴係無色澄清。該等浴之溫度係維持於30℃,且來自250瓦鹵燈之光係施用至每一晶圓之正面。對每一浴施以0.34伏之電壓。第一浴中所施用之電流密度係2 A/dm2
,第二浴中之電流密度係2.3 A/dm2
,且第三浴中之電流密度係2.5 A/dm2
。施行LIP 7.5分鐘以將銅層沉積於每一晶圓之電流軌道上。將各晶圓自個自之鍍覆槽中移除,以水沖洗,並隨後於室溫空氣乾燥。隨後,將每一晶圓於Ohaus EO2140分析天平上稱重。重量係記錄於下表II中。
來自酸性二價銅浴之銅平均鍍覆速率測定為6.42 mg/分鐘。與之相對,來自鹼性一價銅鍍覆浴之銅平均鍍覆速率為12.85 mg/分鐘。鍍覆結果顯示,藉由LIP自鹼性一價鍍覆浴之銅沉積比藉由LIP自酸性二價銅浴之銅沉積更快。
將含有具銀匯流排之鋁背面的單晶半導體晶圓置於含有ENLIGHTTM
420電解銅鍍覆浴之鍍覆槽內。該浴係酸性二價銅離子浴。該浴之溫度係30℃。不施用電流,且遮蔽該鍍覆槽以防止該槽曝露於任何光(包括周邊室內光線)中。8分鐘後,於該銀匯流排上觀察到銅之沉積,表明藉由浸沒鍍覆將銅鍍於該匯流排上。
將含有具銀匯流排之鋁背面的第二片單晶半導體晶
圓置於含有上述實施例1至6中表I中顯示之一價銅鍍覆浴中。該浴之溫度係30℃。不施用電流,且遮蔽該鍍覆槽以防止該槽曝露於任何光(包括周邊室內光線)中。於該浴中停留8分鐘後,未於該銀匯流排上或於該鋁塗層上觀察到銅沉積。該一價銅鍍覆浴未顯示任何可觀察之如該酸性二價銅浴者的非所欲之浸沒銅鍍覆。
提供其正面具有稜錐狀突起之摻雜單晶矽晶圓。該晶圓之正面具有n+摻雜區域,形成射極層。於該射極層下,該晶圓具有PN接面。該晶圓之正面係塗佈有由Si3
N4
組成之鈍化層或抗反射層。該正面亦具有透過該抗反射層而曝露該晶圓之表面之電流軌道圖案。每一電流軌道係橫貫該晶圓之整體長度。於該晶圓之一末端及該晶圓之中心處,該等電流軌道併入匯流排。該背面係經p+摻雜,且係含有鋁電極及銀匯流排。將該晶圓置於金屬鍍覆架上,使其背面鋁電極及匯流排直接接觸該金屬鍍覆架。該槽與架之介面係沿著該晶圓之邊緣予以密封,以最小化溶液對該槽之背面與鍍覆架之間的滲透。以5wt%過氧化氫水溶液氧化該電流軌道及匯流排,以確保該矽表面係經氧化。
隨後,將該晶圓浸沒於鍍覆槽內之包括15 g/L之酸式氟化鈉及30 g/L胺磺酸之水溶液中。將其上裝備晶圓之架連結至整流器,且使用鉑線作為相對電極。該水溶液、晶圓及鉑線係彼此電性連通。以中等程度攪動該組成物並將其保持於室溫。最初,於1.2V對該晶圓施用2秒之0.1
A/dm2
的陽極電流,隨後,將該電流切斷1秒。將該陽極電流至0之電流脈動重複30次循環。將該晶圓之正面上的電流軌道及匯流排蝕刻以形成實質均勻之奈米孔射極層之後,自該水溶液移除該槽,並以去離子水沖洗。
隨後,將經摻雜之單晶矽晶圓浸沒於含有NIKALTM
電解鎳鍍覆化學質之鍍覆槽內。將裝備該晶圓之架連結至整流器,且固體鎳陽極係於該浴中用作相對電極。該晶圓係用作陰極。該浴、晶圓及相對電極係全部電性連通,且施用1分鐘之1 A/dm2
的陰極電流。於整個鍍覆循環中,係將人工光施用至該晶圓。該光源係250瓦鹵燈。鍍覆溫度係自30℃至50℃之範圍。持續鍍覆直至厚度為300nm之鎳種子層係沉積於該電流軌道及匯流排中。
隨後,將鍍覆有鎳之晶圓置於具有下表之配方的一價銅鍍覆浴中。
以氫氧化鈉將該浴之pH調節至8。將該浴之溫度維持於45℃。施用磁力攪拌器攪動該浴。
將裝備晶圓之架連結至整流器,且經磷化之銅可溶性陽極係於該浴中用作相對電極。該浴、晶圓及相對電極係
全部電性連通,施用10分鐘之密度為2 A/dm2
的陰極電流,以於每一電流軌道及匯流排之鎳種子層上沉積厚度為10μm之銅層。於鍍覆過程中,係將人工光施用至該晶圓。該光源係250瓦鹵燈。不預期於該背面銀匯流排上出現銅鍍覆。
Claims (9)
- 一種方法,係包含:a)提供半導體,其係包含正面、背面及PN接面,該正面係包含導電軌道之圖案,該導電軌道之圖案係包含下方層,且該背面係包括金屬接觸;b)將該半導體與一價銅鍍覆組成物接觸;以及c)將銅層鍍覆於該導電軌道之該下方層上。
- 如申請專利範圍第1項所述之方法,其中,該銅係藉由電解電鍍或光誘導鍍覆而鍍覆者。
- 如申請專利範圍第1項所述之方法,其中,該下方層係包含選自鎳、鈷、鈀、銀或鉬之金屬。
- 如申請專利範圍第1項所述之方法,其中,該下方層係金屬矽化物。
- 如申請專利範圍第1項所述之方法,其中,該一價銅鍍覆組成物係包含一種或多種還原劑。
- 如申請專利範圍第1項所述之方法,其中,該一價銅鍍覆組成物係包含選自氧化銅、硫酸銅及甲磺酸銅之一種或多種銅離子源。
- 如申請專利範圍第1項所述之方法,其中,該銅層係1μm至50μm厚。
- 如申請專利範圍第1項所述之方法,係復包含將金屬飾層或有機保焊劑沉積於該銅層上。
- 如申請專利範圍第1項所述之方法,其中,該一價銅鍍覆組成物之pH係7至12。
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JP6367322B2 (ja) * | 2013-06-17 | 2018-08-01 | アプライド マテリアルズ インコーポレイテッドApplied Materials,Incorporated | 湿式ウエハバックコンタクトを使用したシリコンビアを通した銅メッキのための方法 |
CN104711648B (zh) * | 2013-12-17 | 2019-08-16 | Ykk株式会社 | 闪镀铜镀敷液 |
TWI638424B (zh) * | 2014-11-10 | 2018-10-11 | 應用材料股份有限公司 | 利用濕式晶圓背側接觸進行銅電鍍矽穿孔的方法 |
CN105154936A (zh) * | 2015-08-21 | 2015-12-16 | 无锡桥阳机械制造有限公司 | 一种稀土镧-铜-锌合金电镀液及其电镀方法 |
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