US20090120799A1 - Multiple-step electrodeposition process for direct copper plating on barrier metals - Google Patents
Multiple-step electrodeposition process for direct copper plating on barrier metals Download PDFInfo
- Publication number
- US20090120799A1 US20090120799A1 US12/332,882 US33288208A US2009120799A1 US 20090120799 A1 US20090120799 A1 US 20090120799A1 US 33288208 A US33288208 A US 33288208A US 2009120799 A1 US2009120799 A1 US 2009120799A1
- Authority
- US
- United States
- Prior art keywords
- copper
- layer
- substrate
- seed layer
- barrier layer
- 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.)
- Abandoned
Links
- 239000010949 copper Substances 0.000 title claims abstract description 120
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 66
- 230000004888 barrier function Effects 0.000 title claims abstract description 58
- 238000007747 plating Methods 0.000 title description 64
- 229910052751 metal Inorganic materials 0.000 title description 19
- 239000002184 metal Substances 0.000 title description 19
- 150000002739 metals Chemical class 0.000 title description 4
- 238000004070 electrodeposition Methods 0.000 title 1
- 239000000758 substrate Substances 0.000 claims abstract description 69
- 238000000151 deposition Methods 0.000 claims abstract description 36
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 31
- 230000008021 deposition Effects 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 238000009713 electroplating Methods 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- -1 tungsten nitride Chemical class 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 claims description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 2
- DOVLHZIEMGDZIW-UHFFFAOYSA-N [Cu+3].[O-]B([O-])[O-] Chemical compound [Cu+3].[O-]B([O-])[O-] DOVLHZIEMGDZIW-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 74
- 150000001875 compounds Chemical class 0.000 description 34
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 229910000365 copper sulfate Inorganic materials 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000012545 processing Methods 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 230000000536 complexating effect Effects 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 9
- 239000003446 ligand Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000005240 physical vapour deposition Methods 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 239000000080 wetting agent Substances 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- 239000002738 chelating agent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000000231 atomic layer deposition Methods 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000007772 electroless plating Methods 0.000 description 5
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 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 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 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 3
- 239000001509 sodium citrate Substances 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
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 241000393496 Electra Species 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940079895 copper edta Drugs 0.000 description 2
- BDXBEDXBWNPQNP-UHFFFAOYSA-L copper;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron Chemical compound [Cu+2].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O BDXBEDXBWNPQNP-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
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- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- 229960002635 potassium citrate Drugs 0.000 description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 2
- 235000011082 potassium citrates Nutrition 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 1
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- 238000011109 contamination Methods 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- UZLGHNUASUZUOR-UHFFFAOYSA-L dipotassium;3-carboxy-3-hydroxypentanedioate Chemical compound [K+].[K+].OC(=O)CC(O)(C([O-])=O)CC([O-])=O UZLGHNUASUZUOR-UHFFFAOYSA-L 0.000 description 1
- CVOQYKPWIVSMDC-UHFFFAOYSA-L dipotassium;butanedioate Chemical compound [K+].[K+].[O-]C(=O)CCC([O-])=O CVOQYKPWIVSMDC-UHFFFAOYSA-L 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
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- 229940116315 oxalic acid Drugs 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
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- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 229960003975 potassium Drugs 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940095574 propionic acid Drugs 0.000 description 1
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- 229940107700 pyruvic acid Drugs 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
- H01L21/76864—Thermal treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76868—Forming or treating discontinuous thin films, e.g. repair, enhancement or reinforcement of discontinuous thin films
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
Definitions
- Embodiments of the present invention generally relate to a method to deposit a metal layer with electrochemical plating and more particularly, the metal layer is a copper seed layer.
- Metallization for sub-quarter micron sized features is a foundational technology for present and future generations of integrated circuit manufacturing processes.
- the multilevel interconnects that lie at the heart of these devices are generally formed by filling high aspect ratio interconnect features with a conductive material (e.g., copper or aluminum).
- a conductive material e.g., copper or aluminum.
- CVD chemical vapor deposition
- PVD physical vapor deposition
- plating techniques such as electrochemical plating (ECP) and electroless plating have emerged as viable processes for filling sub-quarter micron sized high aspect ratio interconnect features in integrated circuit manufacturing processes.
- ECP processes are generally two stage processes, wherein a seed layer is first formed over the surface features of the substrate (this process may be performed in a separate system), and then the substrate surface features are exposed to an electrolyte solution while an electrical bias is simultaneously applied between the substrate and an anode positioned within the electrolyte solution.
- the electrolyte solution is generally rich in ions to be plated onto the surface of the substrate. Therefore, the application of the electrical bias drives a reductive reaction to reduce the metal ions and precipitate the respective metal. Upon precipitating, the metal plates onto the seed layer to form a film.
- a thick copper layer (e.g., >200 ⁇ ) over the field is generally needed to have continuous sidewall coverage throughout the depth of the features, which often causes the throat of the feature to close before the feature sidewalls are covered. Additionally, copper purity is generally questionable in CVD processes due to difficult complete precursor-ligand removal. ALD techniques, though capable of giving generally conformal deposition with good adhesion to the barrier, take too much time to give a continuous copper film on the sidewalls. Also, alternative materials that include cobalt, nickel, ruthenium, silver and titanium nitride are gradually replacing materials used for barrier layers.
- barrier materials such as tantalum or tantalum nitride
- barrier materials such as tantalum or tantalum nitride
- conductive barrier materials e.g., cobalt
- PVD has been a preferred technique to deposit a copper seed layer.
- Electroless plating techniques for depositing a seed layer onto a barrier layer of tantalum or tantalum nitride are known.
- a well adhered seed layer has several benefits, such as protecting the barrier layer (e.g., cobalt) from the acidic solutions utilized during the electroplating of the bulk copper layer. Also, the copper seed supports the bulk copper and minimizes peeling from the barrier layer.
- the barrier layer e.g., cobalt
- a process for depositing a copper seed layer onto a barrier layer such as cobalt, nickel, ruthenium, silver or titanium nitride.
- the process should deposit the copper seed layer with a strong adhesion to the barrier layer and with good uniformity over the entire substrate surface. Also, the process should be applicable to a range of barrier materials.
- the barrier layers should be maintained with little or no oxidation during the seed layer deposition.
- the present invention generally provides a method for depositing a copper seed layer to a substrate surface, wherein the substrate surface includes a barrier layer.
- the method includes placing the substrate surface into a copper solution, wherein the copper solution includes complexed copper ions, applying a current across the substrate surface and reducing the complexed copper ions with the current to deposit the copper seed layer onto the barrier layer.
- the present invention provides a method for depositing a metal seed layer to a barrier layer on a substrate surface.
- the method includes placing the substrate surface into a solution, wherein the solution includes a metal source compound and a complexing compound, forming complexed metal ions within the solution and reducing the complexed metal ions with an electroplating technique to form the metal seed layer.
- the present invention provides a method for electroplating a copper seed layer to a barrier layer from a copper solution.
- the method includes placing a substrate surface including the barrier layer into fluid contact with the copper solution, wherein the copper solution includes copper ions and complexing compounds and reducing the copper ions with a current to form the copper seed layer.
- FIG. 1 is a top plan view of an embodiment of an electrochemical processing system capable of implementing the method of the invention.
- FIG. 2 is a graph of a current density verses electrical potential.
- One embodiment of the invention teaches a method for depositing a copper seed layer onto a substrate surface, generally onto a barrier layer.
- the method includes placing the substrate surface into a copper solution which includes completed copper ions.
- a current or bias is applied across the substrate surface and the complexed copper ions are reduced to deposit the copper onto the barrier layer.
- the complexed copper ions include a carboxylate ligand, such as citrate, oxalate, tartrate, EDTA and/or acetate.
- the barrier layer includes a metal selected from cobalt, ruthenium, nickel, tungsten, titanium and/or silver.
- the copper solution may also contain wetting agent or suppressor.
- FIG. 1 is a top plan view of an embodiment of an electrochemical processing system (ECPS) 100 capable of implementing the methodology of the present invention.
- the ECPS 100 generally includes a processing base 113 having a robot 120 centrally positioned thereon.
- the robot 120 generally includes one or more robot arms 122 and 124 configured to support substrates thereon. Additionally, the robot 120 and the robot arms 122 and 124 are generally configured extend, rotate and vertically move so that the robot 120 may insert and remove substrates to and from a plurality of processing locations 102 , 104 , 106 , 108 , 110 , 112 , 114 and 116 positioned on the base 113 .
- Processing locations may be configured as electroless plating cells, electrochemical plating cells, substrate rinsing and/or drying cells, substrate bevel clean cells, substrate surface clean or preclean cells and/or other processing cells that are advantageous to plating processes.
- embodiments of the present invention are conducted within at least one of the processing locations 102 , 104 , 110 and 112 .
- the ECPS 100 further includes a factory interface (FI) 130 .
- the FI 130 generally includes at least one FI robot 132 positioned adjacent a side of the FI 130 that is adjacent the processing base 113 .
- the FI robot 132 is positioned to access a substrate 126 from a substrate cassettes 134 .
- the FI robot 132 delivers the substrate 126 to one of processing cells 114 and 116 to initiate a processing sequence.
- FI robot 132 may be used to retrieve substrates from one of the processing cells 114 and 116 after a substrate processing sequence is complete. In this situation FI robot 132 may deliver the substrate 126 back to one of the cassettes 134 for removal from the system 100 .
- robot 132 also extends into a link tunnel 115 that connects factory interface 130 to processing mainframe or platform 113 .
- FI robot 132 is configured to access an anneal chamber 135 positioned in communication with the FI 130 .
- the anneal chamber 135 generally includes a two position annealing chamber, wherein a cooling plate or position 136 and a heating plate or position 137 are positioned adjacently with a substrate transfer robot 140 positioned proximate thereto, e.g., between the two stations.
- the robot 140 is generally configured to move substrates between the respective heating 137 and cooling plates 136 .
- Embodiments of the invention teach the use of complexed copper sources contained within a plating solution for the ECP of copper seed layers.
- a plating solution containing complexed copper sources has a significantly more negative deposition potential than does a plating solution containing free copper ions.
- complexed copper ions have a deposition potential from about ⁇ 0.9 V to about ⁇ 0.3 V, while free copper ions have deposition potentials in the range from about ⁇ 0.3 V to about ⁇ 0.1 V, when referenced to Ag/AgCl (1 M KCl), which has a potential of 20.235 V verses a standard hydrogen electrode.
- Ag/AgCl (1 M KCl which has a potential of 20.235 V verses a standard hydrogen electrode.
- Barrier layers such as cobalt or nickel, have a dissolution potential in the same potential range as the deposition potential of the free copper ions. For example:
- a cobalt or nickel barrier layer is oxidized and dissolved into the solution. Once the integrity of the barrier layer is weakened, copper can migrate through the voids of the barrier layer and contaminate other materials of the substrate.
- FIG. 2 is a graph representing one example of the ECP of complexed copper ions (e.g., Cu-citrate) compared to free-copper ions (e.g., CuSO 4 ).
- the graph plots current density (A/cm 2 ) against potential (V) for a plating process.
- Solutions containing complexed copper ions are labeled as Cu-citrate(1) and Cu-citrate(2).
- the Cu-citrate(1) solution contains 0.25 M copper (II) citrate and 0.25 M sodium citrate, while the Cu-citrate(2) solution contains 0.25 M CuSO 4 and 0.5 M sodium citrate.
- Solutions containing free-copper ions are labeled as CuSO 4 (1) and CuSO 4 (2).
- the CuSO 4 (1) solution contains 0.8 M CuSO 4 and a suppressor, while the CuSO 4 (2) solution contains 0.8 M CuSO 4 , a suppressor and an accelerator.
- the graph demonstrates that by using the complex bath, the copper deposition potential, under any practical current density of 1 mA/cm 2 or greater, shifted significantly to more negative values which result in no cobalt or nickel dissolution/corrosion, as the dissolution potential for these metals is outside of in the range. If less negative values of the copper deposition potential are used, barrier layer oxidation is commenced before a seed layer forms. Hence, the barrier metals are being protected during copper deposition in complex baths via a copper seed layer with potentials of more negative values.
- the current dependence on potential for the complex bath is substantially reduced when compared to the bath with free copper ions. Therefore, the local current density variation across the substrate surface will be improved, even in the presence of a large potential gradient across the substrate surface due to the low electrical conductivity of thin barrier metals. This leads to better deposition uniformity across the substrate surface.
- Suitable barrier layers to deposit metal seed layers (e.g., copper) upon include cobalt, ruthenium, nickel, tungsten, tungsten nitride, titanium, titanium nitride, and silver.
- Barrier layers are generally deposited by chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), high density plasma CVD (HDP-CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), electro- or electroless plating deposition techniques and combinations thereof.
- the deposition process initiates with a bias at a more negative potential (e.g., ⁇ 0.5 V to ⁇ 0.3 V) than required to deposit copper from free copper ions.
- the bias has a more negative potential than required to oxidize the barrier layer.
- the complexed copper ions are chemically reduced and copper metal precipitates from the plating solution.
- the copper precipitate deposits or coats the barrier layer to form the copper seed layer.
- the deposition bias generally has a current density of about 10 mA/cm 2 or less, preferably about 5 mA/cm 2 or less, more preferably at about 3 mA/cm 2 or less. In one embodiment, the deposition bias has a current density in the range from about 0.5 mA/cm 2 to about 3.0 mA/cm 2 .
- Suitable plating solutions that may be used with the processes described herein to plate copper may include at least one acid based electrolyte, at least one copper source compound, at least one chelating or complexing compound, optional wetting agents or suppressors, optional one or more pH adjusting agents and a solvent.
- Plating solutions contain at least one copper source compound complexed or chelated with at least one of a variety of ligands.
- Complexed copper includes a copper atom in the nucleus and surrounded by ligands, functional groups, molecules or ions with a strong finite to the copper, as opposed to free copper ions with very low finite, if any, to a ligand (e.g., water).
- Complexed copper sources are either chelated before being added to the plating solution (e.g., copper citrate) or are formed in situ by combining a free copper ion source (e.g., copper sulfate) with a complexing agent (e.g., citric acid or sodium citrate).
- the copper atom may be in any oxidation state, such as 0, 1 or 2, before, during or after complexing with a ligand. Therefore, throughout the disclosure, the use of the word copper or elemental symbol Cu includes the use of copper metal (Cu 0 ), cupric (Cu +1 ) or cuprous (Cu +2 ), unless otherwise distinguished or noted.
- copper source compounds include copper sulfate, copper phosphate, copper nitrate, copper citrate, copper tartrate, copper oxalate, copper EDTA, copper acetate, copper pyrophosphorate and combinations thereof, preferably copper sulfate and/or copper citrate.
- a particular copper source compound may have ligated varieties.
- copper citrate may include at least one cupric atom, cuprous atom or combinations thereof and at least one citrate ligand and include Cu(C 6 H 7 O 7 ), Cu 2 (C 6 H 4 O 7 ), Cu 3 (C 6 H 5 O 7 ) or Cu(C 6 H 7 O 7 ) 2 .
- copper EDTA may include at least one cupric atom, cuprous atom or combinations thereof and at least one EDTA ligand and include Cu(C 10 H 15 O 8 N 2 ), Cu 2 (C 10 H 14 O 8 N 2 ), Cu 3 (C 10 H 13 O 8 N 2 ), Cu 4 (C 10 H 12 O 8 N 2 ), Cu(C 10 H 14 O 8 N 2 ) or Cu 2 (C 10 H 12 O 8 N 2 ).
- the plating solution may include one or more copper source compounds or complexed metal compounds at a concentration in the range from about 0.02 M to about 0.8 M, preferably in the range from about 0.1 M to about 0.5 M. For example, about 0.25 M of copper sulfate may be used as a copper source compounds.
- the plating solution contains one or more chelating or complexing compounds and include compounds having one or more functional groups selected from the group of carboxylate groups, hydroxyl groups, alkoxyl, oxo acids groups, mixture of hydroxyl and carboxylate groups and combinations thereof.
- suitable chelating compounds having one or more carboxylate groups include citric acid, tartaric acid, pyrophosphoric acid, succinic acid, oxalic acid, and combinations thereof.
- Suitable acids having one or more carboxylate groups include acetic acid, adipic acid, butyric acid, capric acid, caproic acid, caprylic acid, glutaric acid, glycolic acid, formic acid, fumaric acid, lactic acid, lauric acid, malic acid, maleic acid, malonic acid, myristic acid, plamitic acid, phthalic acid, propionic acid, pyruvic acid, stearic acid, valeric acid, quinaldine acid, glycine, anthranilic acid, phenylalanine and combinations thereof.
- suitable chelating compounds include compounds having one or more amine and amide functional groups, such as ethylenediamine, diethylenetriamine, diethylenetriamine derivatives, hexadiamine, amino acids, ethylenediaminetetraacetic acid, methylformamide or combinations thereof.
- the plating solution may include one or more chelating agents at a concentration in the range from about 0.02 M to about 1.6 M, preferably in the range from about 0.2 M to about 1.0 M. For example, about 0.5 M of citric acid may be used as a chelating agent.
- the one or more chelating compounds may also include salts of the chelating compounds described herein, such as lithium, sodium, potassium, cesium, calcium, magnesium, ammonium and combinations thereof.
- Such salt combines with a copper source to produce NaCu(C 6 H 5 O 7 ).
- suitable inorganic or organic acid salts include ammonium and potassium salts or organic acids, such as ammonium oxalate, ammonium citrate, ammonium succinate, monobasic potassium citrate, dibasic potassium citrate, tribasic potassium citrate, potassium tartrate, ammonium tartrate, potassium succinate, potassium oxalate, and combinations thereof.
- the one or more chelating compounds may also include complexed salts, such as hydrates (e.g., sodium citrate dihydrate).
- plating solutions are particularly useful for plating copper, it is believed that the solutions also may be used for depositing other conductive materials, such as platinum, tungsten, titanium, cobalt, gold, silver, ruthenium and combinations thereof.
- a copper precursor is substituted by a precursor containing the aforementioned metal and at least one ligand, such as cobalt citrate, cobalt sulfate or cobalt phosphate.
- Wetting agents or suppressors such as electrically resistive additives that reduce the conductivity of the plating solution may be added to the solution in a range from about 10 ppm to about 2,000 ppm, preferably in a range from about 50 ppm to about 1,000 ppm.
- Suppressors include polyacrylamide, polyacrylic acid polymers, polycarboxylate copolymers, polyethers or polyesters of ethylene oxide and/or propylene oxide (EO/PO), coconut diethanolamide, oleic diethanolamide, ethanolamide derivatives or combinations thereof.
- One or more pH-adjusting agents are optionally added to the plating solution to achieve a pH less than 7, preferably between about 3 and about 7, more preferably between about 4.5 and about 6.5.
- the amount of pH adjusting agent can vary as the concentration of the other components is varied in different formulations. Different compounds may provide different pH levels for a given concentration, for example, the composition may include between about 0.1% and about 10% by volume of a base, such as potassium hydroxide, ammonium hydroxide or combinations thereof, to provide the desired pH level.
- the one or more pH adjusting agents can be chosen from a class of acids including, carboxylic acids, such as acetic acid, citric acid, oxalic acid, phosphate-containing components including phosphoric acid, ammonium phosphates, potassium phosphates, inorganic acids, such as sulfuric acid, nitric acid, hydrochloric acid and combinations thereof.
- carboxylic acids such as acetic acid, citric acid, oxalic acid
- phosphate-containing components including phosphoric acid, ammonium phosphates, potassium phosphates
- inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid and combinations thereof.
- the balance or remainder of the plating solution described herein is a solvent, such as a polar solvent.
- a solvent such as a polar solvent.
- Water is a preferred solvent, preferably deionized water.
- Organic solvents, for example, alcohols or glycols, may also be used, but are generally included in an aqueous solution.
- the plating solution may include one or more additive compounds.
- Additive compounds include electrolyte additives including, but not limited to, suppressors, enhancers, levelers, brighteners and stabilizers to improve the effectiveness of the plating solution for depositing metal, namely copper to the substrate surface.
- certain additives may decrease the ionization rate of the metal atoms, thereby inhibiting the dissolution process, whereas other additives may provide a finished, shiny substrate surface.
- the additives may be present in the plating solution in concentrations up to about 15% by weight or volume, and may vary based upon the desired result after plating.
- a plating solution includes at least one copper source compound, at least one chelating or complexing compound and solvent.
- the at least one copper source compound includes copper sulfate
- the chelating compound includes citrate salt
- the solvent is deionized Water. Copper sulfate is dissolved in deionized water to produce a copper sulfate solution with a concentration of about 0.25 M.
- sodium citrate dihydrate is dissolved in deionized water to solution with a concentration of about 0.5 M.
- the two aforementioned solutions are combined to form a plating solution with a pH in the range from about 5 to about 6.
- the copper source e.g., copper sulfate
- the chelating compound e.g., sodium citrate dihydrate
- a plating solution includes at least one copper source compound, at least one chelating or complexing compound, at least one wetting agent and solvent.
- the at least one copper source compound includes copper sulfate
- the chelating compound includes a citrate salt
- the wetting agent includes copolymers of ethylene oxide and propylene oxide
- the solvent is deionized water.
- the copper sulfate and the citrate solutions of above are combined with about 200 ppm of the copolymer (ethylene and propylene oxides) to form a plating solution with a pH in the range from about 5 to about 6.
- a plating solution includes at least one copper source compound, at least one chelating or complexing compound and solvent.
- the at least one copper source compound includes copper sulfate
- the chelating compound includes boric acid
- the solvent is deionized water.
- Copper sulfate is dissolved in boric acid to form a plating solution with a pH in the range from about 5 to about 6.
- the copper sulfate has a concentration of about 0.25 M and the boric acid has a concentration of about 0.40 M.
- a plating solution includes at least one copper source compound, at least one chelating or complexing compound, at least one wetting agent and solvent.
- the at least one copper source compound includes copper sulfate
- the chelating compound includes a citrate salt
- the wetting agent includes copolymers of ethylene oxide and propylene oxide
- the solvent is deionized water.
- the copper sulfate and the citrate solutions of above are combined with the copolymer (ethylene and propylene oxides) to form a plating solution with a pH in the range from about 5 to about 6.
- the copper seed is deposited using any of the aforementioned plating solutions within a cell on the Electra Cu ECP® system or the SlimCell Copper Plating system, both of which are available from Applied Materials, Inc. of Santa Clara, Calif.
- the plating cells of these systems, or other plating systems utilized may be modified to allow a more uniform electric field than produced from the standard cell.
- One adjustment includes the replacement of the solid anode with a segmented anode.
- a shutter or shield is added to the cell to direct current in a more uniform field about the substrate surface.
- the substrate surface, containing a barrier layer, is exposed to a plating solution.
- a bias commences from the anode, on the bottom of the cell, through the plating solution and across the substrate surface.
- the voltage is generally kept constant though the process at a range from about ⁇ 0.9 V to about ⁇ 0.3 V, such that the current density across the substrate surface is about 10 mA/cm 2 or less, preferably about 3 mA/cm 2 or less.
- the copper seed layer is deposited as the voltage or current reduces the complexed copper ions within the plating solution.
- the copper seed layer is deposited to a thickness in a range from about 50 ⁇ to about 300 ⁇ . In one aspect, the thickness is about 300 ⁇ or less, preferably at about 200 ⁇ or less and more preferably, at about 100 ⁇ or less.
- the substrate is rinsed to eliminate contamination of subsequent plating solutions by the copper plating solution.
- the substrate is rinsed with an aqueous solution, preferably deionized water, for a period from about 5 seconds to about 30 seconds, while rotating at a rate from about 20 rpm to about 400 rpm.
- the substrate is dried via gas flow, such as nitrogen, argon, helium, hydrogen or combinations thereof.
- the substrate is annealed, preferably thermally annealed in an environment containing hydrogen gas, to obtain a better crystal orientation. Better crystal orientations improve electromigration resistance of the subsequent copper migration.
- the substrate is placed into a rapid thermal process (RTP) chamber, such as the RTP XEplus Centura® or the anneal chamber of the Electra iECP® or SlimCell plating systems, both of which are available from Applied Materials, Inc. of Santa Clara, Calif.
- the chamber is generally an oxygen-free environment, usually containing a gas, such as nitrogen, argon, helium, hydrogen or combinations thereof.
- the substrate is annealed for a period in the range from about 5 seconds to about 180 seconds at a temperature in the range from about 150° C. to about 350° C. The annealing duration may also be between about 5 seconds and about 20 seconds.
- the gap-fill step includes a solution containing about 0.05-0.5 M H 2 SO 4 , about 20-100 ppm level of CI, about 8-24 ppm SPS (an accelerator), about 50-500 ppm co-polymer of ethylene oxide and propylene oxide (EO/PO co-polymer as wetting agents) and less than about 100 ppm polyamine as a leveler.
- a second annealing step is performed, followed by a third copper deposition step, which is a bulk-fill step.
- the bulk-fill step includes a deposition solution that was made by adding at least one leveling agent (e.g., polyamine or polyimidazole) to the solution used during the gap-fill deposition.
- the leveling agent is used to achieve a better planarization. Also, pulsed, reversed current can be introduced to fine-tune the planarity of the final copper deposition.
- a copper seed layer was deposited onto a substrate containing a barrier layer (cobalt).
- the copper seed was deposited using the following plating solution within a modified cell on the Electra Cu ECP® system.
- a substrate was disposed in a basin containing a plating solution of:
- the plating solution had a pH of about 6. Electricity was applied at a current density of about 2 mA/cm 2 . The plating process continued until the seed layer was deposited to a thickness of about 100 ⁇ .
- the substrate was rinsed in deionized water for about 30 seconds while rotating at about 100 rpm and then dried via an argon gas flow.
- the substrate was annealed in an O 2 -free environment for 30 seconds, in the annealing chamber of the Electra iECP system.
- the gap-fill step includes a solution containing CuSO 4 (0.25 M), H 2 SO 4 (0.3 M), 50 ppm level of CI, 15 ppm SPS (an accelerator), 200 ppm of EO/PO co-polymer of mean molecular weight of 5,000.
- the bulk-fill step includes a deposition solution made by adding polyamine (a leveling agent) to the solution used during the gap-fill.
- a copper seed layer was deposited onto a substrate containing a barrier layer (cobalt).
- the copper seed was deposited using the following plating solution within a modified cell on the Electra Cu ECP® system.
- a substrate was disposed in a basin containing a plating solution of:
- the plating solution had a pH of about 5.8. Electricity was applied at a current density of about 2.0 mA/cm 2 . The plating process continued until the seed layer was deposited to a thickness of about 100 ⁇ .
- a copper seed layer was deposited onto a substrate containing a barrier layer (ruthenium).
- the copper seed was deposited using the following plating solution within a modified cell on the Electra Cu ECP® system.
- a substrate was disposed in a basin containing a plating solution of:
- the plating solution had a pH of about 5. Electricity was applied at a current density of about 2.0 mA/cm 2 . The plating process continued until the seed layer was deposited to a thickness of about 100 ⁇ .
- a copper seed layer was deposited onto a substrate containing a barrier layer (ruthenium).
- the copper seed was deposited using the following plating solution within a modified cell on the Electra Cu ECP® system.
- a substrate was disposed in a basin containing a plating solution of:
- the plating solution had a pH of about 5. Electricity was applied at a current density of about 2.0 mA/cm 2 . The plating process continued until the seed layer was deposited to a thickness of about 100 ⁇ .
- a copper seed layer was deposited onto several substrates containing a cobalt barrier layer consistent to the procedure of Example 1.
- the substrates were examined by various means upon commencing the plating process with a seed layer thickness of about 100 ⁇ .
- a tape test determined strong adhesion existed between the barrier layer and the copper seed layer.
- the conductivity of the copper seed layer was qualitatively high. Furthermore, little or no oxidation occurred to the barrier layer during the deposition of the seed layer.
Abstract
Embodiments of the invention teach a method for depositing a copper seed layer to a substrate surface, generally to a barrier layer. The method includes placing the substrate surface into a copper solution, wherein the copper solution includes complexed copper ions. A current or bias is applied across the substrate surface and the complexed copper ions are reduced to deposit the copper seed layer onto the barrier layer.
Description
- This application is a divisional of U.S. patent application Ser. No. 10/616,097, filed Jul. 8, 2003, which is incorporated by reference in its entirety.
- 1. Field of the Invention
- Embodiments of the present invention generally relate to a method to deposit a metal layer with electrochemical plating and more particularly, the metal layer is a copper seed layer.
- 2. Description of the Related Art
- Metallization for sub-quarter micron sized features is a foundational technology for present and future generations of integrated circuit manufacturing processes. In devices such as ultra large scale integration-type devices, i.e., devices having integrated circuits with more than a million logic gates, the multilevel interconnects that lie at the heart of these devices are generally formed by filling high aspect ratio interconnect features with a conductive material (e.g., copper or aluminum). Conventionally, deposition techniques such as chemical vapor deposition (CVD) and physical vapor deposition (PVD) have been used to fill these interconnect features. However, as interconnect sizes decrease and aspect ratios increase, void-free interconnect feature fill via conventional metallization techniques becomes increasingly difficult. As a result thereof, plating techniques, such as electrochemical plating (ECP) and electroless plating have emerged as viable processes for filling sub-quarter micron sized high aspect ratio interconnect features in integrated circuit manufacturing processes.
- In an ECP process sub-quarter micron sized high aspect ratio features formed into the surface of a substrate may be efficiently filled with a conductive material, such as copper. Most ECP processes are generally two stage processes, wherein a seed layer is first formed over the surface features of the substrate (this process may be performed in a separate system), and then the substrate surface features are exposed to an electrolyte solution while an electrical bias is simultaneously applied between the substrate and an anode positioned within the electrolyte solution. The electrolyte solution is generally rich in ions to be plated onto the surface of the substrate. Therefore, the application of the electrical bias drives a reductive reaction to reduce the metal ions and precipitate the respective metal. Upon precipitating, the metal plates onto the seed layer to form a film.
- The process requirements for copper interconnects are becoming more stringent, as the critical dimensions for modern microelectronic devices shrink to 0.1 μm or less. As a result thereof, conventional plating processes will likely be inadequate to support the demands of future interconnect technologies. Conventional plating practices include depositing a copper seed layer via physical vapor deposition (PVD), chemical vapor deposition (CVD) or atomic layer deposition (ALD) onto a diffusion barrier layer (e.g., tantalum or tantalum nitride). However, it is extremely difficult to have adequate seed step coverage with PVD techniques, as discontinuous islands of copper agglomerates are often obtained close to the feature bottom in high aspect ratio features with PVD techniques. For CVD techniques, a thick copper layer (e.g., >200 Å) over the field is generally needed to have continuous sidewall coverage throughout the depth of the features, which often causes the throat of the feature to close before the feature sidewalls are covered. Additionally, copper purity is generally questionable in CVD processes due to difficult complete precursor-ligand removal. ALD techniques, though capable of giving generally conformal deposition with good adhesion to the barrier, take too much time to give a continuous copper film on the sidewalls. Also, alternative materials that include cobalt, nickel, ruthenium, silver and titanium nitride are gradually replacing materials used for barrier layers.
- Direct electroplating on barrier materials, such as tantalum or tantalum nitride, is difficult, since these traditional barrier materials generally have insulating native oxides across the surface. Also during electroplating, conductive barrier materials (e.g., cobalt) generally will oxidize near the reductive potential of free copper ions. Therefore, the integrity of the barrier layer is compromised during the electroplating of a copper seed layer. PVD has been a preferred technique to deposit a copper seed layer. Electroless plating techniques for depositing a seed layer onto a barrier layer of tantalum or tantalum nitride are known. However, these techniques have suffered from several problems, such as adhesion failure between the copper seed layer and the barrier layer, as well as the added complexity of a complete electroless deposition system and the associated difficulties of process control. Furthermore, a well adhered seed layer has several benefits, such as protecting the barrier layer (e.g., cobalt) from the acidic solutions utilized during the electroplating of the bulk copper layer. Also, the copper seed supports the bulk copper and minimizes peeling from the barrier layer.
- Therefore, there is a need for a process for depositing a copper seed layer onto a barrier layer, such as cobalt, nickel, ruthenium, silver or titanium nitride. The process should deposit the copper seed layer with a strong adhesion to the barrier layer and with good uniformity over the entire substrate surface. Also, the process should be applicable to a range of barrier materials. The barrier layers should be maintained with little or no oxidation during the seed layer deposition.
- The present invention generally provides a method for depositing a copper seed layer to a substrate surface, wherein the substrate surface includes a barrier layer. The method includes placing the substrate surface into a copper solution, wherein the copper solution includes complexed copper ions, applying a current across the substrate surface and reducing the complexed copper ions with the current to deposit the copper seed layer onto the barrier layer.
- In another embodiment, the present invention provides a method for depositing a metal seed layer to a barrier layer on a substrate surface. The method includes placing the substrate surface into a solution, wherein the solution includes a metal source compound and a complexing compound, forming complexed metal ions within the solution and reducing the complexed metal ions with an electroplating technique to form the metal seed layer.
- In another embodiment, the present invention provides a method for electroplating a copper seed layer to a barrier layer from a copper solution. The method includes placing a substrate surface including the barrier layer into fluid contact with the copper solution, wherein the copper solution includes copper ions and complexing compounds and reducing the copper ions with a current to form the copper seed layer.
- So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
-
FIG. 1 is a top plan view of an embodiment of an electrochemical processing system capable of implementing the method of the invention; and -
FIG. 2 is a graph of a current density verses electrical potential. - One embodiment of the invention teaches a method for depositing a copper seed layer onto a substrate surface, generally onto a barrier layer. The method includes placing the substrate surface into a copper solution which includes completed copper ions. A current or bias is applied across the substrate surface and the complexed copper ions are reduced to deposit the copper onto the barrier layer. In one aspect, the complexed copper ions include a carboxylate ligand, such as citrate, oxalate, tartrate, EDTA and/or acetate. The barrier layer includes a metal selected from cobalt, ruthenium, nickel, tungsten, titanium and/or silver. The copper solution may also contain wetting agent or suppressor.
-
FIG. 1 is a top plan view of an embodiment of an electrochemical processing system (ECPS) 100 capable of implementing the methodology of the present invention. The ECPS 100 generally includes aprocessing base 113 having arobot 120 centrally positioned thereon. Therobot 120 generally includes one ormore robot arms robot 120 and therobot arms robot 120 may insert and remove substrates to and from a plurality ofprocessing locations base 113. Processing locations may be configured as electroless plating cells, electrochemical plating cells, substrate rinsing and/or drying cells, substrate bevel clean cells, substrate surface clean or preclean cells and/or other processing cells that are advantageous to plating processes. Preferably, embodiments of the present invention are conducted within at least one of theprocessing locations - The ECPS 100 further includes a factory interface (FI) 130. The
FI 130 generally includes at least oneFI robot 132 positioned adjacent a side of theFI 130 that is adjacent theprocessing base 113. TheFI robot 132 is positioned to access asubstrate 126 from asubstrate cassettes 134. TheFI robot 132 delivers thesubstrate 126 to one of processingcells FI robot 132 may be used to retrieve substrates from one of theprocessing cells situation FI robot 132 may deliver thesubstrate 126 back to one of thecassettes 134 for removal from thesystem 100. Further,robot 132 also extends into alink tunnel 115 that connectsfactory interface 130 to processing mainframe orplatform 113. Additionally,FI robot 132 is configured to access ananneal chamber 135 positioned in communication with theFI 130. Theanneal chamber 135 generally includes a two position annealing chamber, wherein a cooling plate orposition 136 and a heating plate orposition 137 are positioned adjacently with asubstrate transfer robot 140 positioned proximate thereto, e.g., between the two stations. Therobot 140 is generally configured to move substrates between therespective heating 137 and coolingplates 136. - Embodiments of the invention teach the use of complexed copper sources contained within a plating solution for the ECP of copper seed layers. A plating solution containing complexed copper sources has a significantly more negative deposition potential than does a plating solution containing free copper ions. Generally, complexed copper ions have a deposition potential from about −0.9 V to about −0.3 V, while free copper ions have deposition potentials in the range from about −0.3 V to about −0.1 V, when referenced to Ag/AgCl (1 M KCl), which has a potential of 20.235 V verses a standard hydrogen electrode. For example:
-
Cu2(C6H4O7)+2H2O→2Cu0+C6H8O7+O2Δε=−0.7 V -
Cu+2+2e −→Cu0Δε=−0.2 V. - Barrier layers, such as cobalt or nickel, have a dissolution potential in the same potential range as the deposition potential of the free copper ions. For example:
-
Cu+2+2e −→Cu0Δε=−0.2 V -
Co0→Co+2+2e −Δε=−0.2 V. - Therefore, while free copper ions are reduced to form the copper seed layer, a cobalt or nickel barrier layer is oxidized and dissolved into the solution. Once the integrity of the barrier layer is weakened, copper can migrate through the voids of the barrier layer and contaminate other materials of the substrate.
-
FIG. 2 is a graph representing one example of the ECP of complexed copper ions (e.g., Cu-citrate) compared to free-copper ions (e.g., CuSO4). The graph plots current density (A/cm2) against potential (V) for a plating process. Solutions containing complexed copper ions are labeled as Cu-citrate(1) and Cu-citrate(2). The Cu-citrate(1) solution contains 0.25 M copper (II) citrate and 0.25 M sodium citrate, while the Cu-citrate(2) solution contains 0.25 M CuSO4 and 0.5 M sodium citrate. Solutions containing free-copper ions are labeled as CuSO4(1) and CuSO4(2). The CuSO4(1) solution contains 0.8 M CuSO4 and a suppressor, while the CuSO4(2) solution contains 0.8 M CuSO4, a suppressor and an accelerator. The graph demonstrates that by using the complex bath, the copper deposition potential, under any practical current density of 1 mA/cm2 or greater, shifted significantly to more negative values which result in no cobalt or nickel dissolution/corrosion, as the dissolution potential for these metals is outside of in the range. If less negative values of the copper deposition potential are used, barrier layer oxidation is commenced before a seed layer forms. Hence, the barrier metals are being protected during copper deposition in complex baths via a copper seed layer with potentials of more negative values. - On the other hand, the current dependence on potential for the complex bath is substantially reduced when compared to the bath with free copper ions. Therefore, the local current density variation across the substrate surface will be improved, even in the presence of a large potential gradient across the substrate surface due to the low electrical conductivity of thin barrier metals. This leads to better deposition uniformity across the substrate surface.
- Suitable barrier layers to deposit metal seed layers (e.g., copper) upon include cobalt, ruthenium, nickel, tungsten, tungsten nitride, titanium, titanium nitride, and silver. Barrier layers are generally deposited by chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), high density plasma CVD (HDP-CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), electro- or electroless plating deposition techniques and combinations thereof.
- Since the plating solution includes complexed copper ions, the deposition process initiates with a bias at a more negative potential (e.g., −0.5 V to −0.3 V) than required to deposit copper from free copper ions. Also, the bias has a more negative potential than required to oxidize the barrier layer. As the bias is applied, the complexed copper ions are chemically reduced and copper metal precipitates from the plating solution. The copper precipitate deposits or coats the barrier layer to form the copper seed layer. Once the barrier layer has a copper seed layer deposited upon, the barrier layer is protected or shielded from metal dissolution processes at less negative potentials. The deposition bias generally has a current density of about 10 mA/cm2 or less, preferably about 5 mA/cm2 or less, more preferably at about 3 mA/cm2 or less. In one embodiment, the deposition bias has a current density in the range from about 0.5 mA/cm2 to about 3.0 mA/cm2.
- Suitable plating solutions that may be used with the processes described herein to plate copper may include at least one acid based electrolyte, at least one copper source compound, at least one chelating or complexing compound, optional wetting agents or suppressors, optional one or more pH adjusting agents and a solvent.
- Plating solutions contain at least one copper source compound complexed or chelated with at least one of a variety of ligands. Complexed copper includes a copper atom in the nucleus and surrounded by ligands, functional groups, molecules or ions with a strong finite to the copper, as opposed to free copper ions with very low finite, if any, to a ligand (e.g., water). Complexed copper sources are either chelated before being added to the plating solution (e.g., copper citrate) or are formed in situ by combining a free copper ion source (e.g., copper sulfate) with a complexing agent (e.g., citric acid or sodium citrate). The copper atom may be in any oxidation state, such as 0, 1 or 2, before, during or after complexing with a ligand. Therefore, throughout the disclosure, the use of the word copper or elemental symbol Cu includes the use of copper metal (Cu0), cupric (Cu+1) or cuprous (Cu+2), unless otherwise distinguished or noted.
- Examples of suitable copper source compounds include copper sulfate, copper phosphate, copper nitrate, copper citrate, copper tartrate, copper oxalate, copper EDTA, copper acetate, copper pyrophosphorate and combinations thereof, preferably copper sulfate and/or copper citrate. A particular copper source compound may have ligated varieties. For example, copper citrate may include at least one cupric atom, cuprous atom or combinations thereof and at least one citrate ligand and include Cu(C6H7O7), Cu2(C6H4O7), Cu3(C6H5O7) or Cu(C6H7O7)2. In another example, copper EDTA may include at least one cupric atom, cuprous atom or combinations thereof and at least one EDTA ligand and include Cu(C10H15O8N2), Cu2(C10H14O8N2), Cu3(C10H13O8N2), Cu4(C10H12O8N2), Cu(C10H14O8N2) or Cu2(C10H12O8N2). The plating solution may include one or more copper source compounds or complexed metal compounds at a concentration in the range from about 0.02 M to about 0.8 M, preferably in the range from about 0.1 M to about 0.5 M. For example, about 0.25 M of copper sulfate may be used as a copper source compounds.
- The plating solution contains one or more chelating or complexing compounds and include compounds having one or more functional groups selected from the group of carboxylate groups, hydroxyl groups, alkoxyl, oxo acids groups, mixture of hydroxyl and carboxylate groups and combinations thereof. Examples of suitable chelating compounds having one or more carboxylate groups include citric acid, tartaric acid, pyrophosphoric acid, succinic acid, oxalic acid, and combinations thereof. Other suitable acids having one or more carboxylate groups include acetic acid, adipic acid, butyric acid, capric acid, caproic acid, caprylic acid, glutaric acid, glycolic acid, formic acid, fumaric acid, lactic acid, lauric acid, malic acid, maleic acid, malonic acid, myristic acid, plamitic acid, phthalic acid, propionic acid, pyruvic acid, stearic acid, valeric acid, quinaldine acid, glycine, anthranilic acid, phenylalanine and combinations thereof. Further examples of suitable chelating compounds include compounds having one or more amine and amide functional groups, such as ethylenediamine, diethylenetriamine, diethylenetriamine derivatives, hexadiamine, amino acids, ethylenediaminetetraacetic acid, methylformamide or combinations thereof. The plating solution may include one or more chelating agents at a concentration in the range from about 0.02 M to about 1.6 M, preferably in the range from about 0.2 M to about 1.0 M. For example, about 0.5 M of citric acid may be used as a chelating agent.
- The one or more chelating compounds may also include salts of the chelating compounds described herein, such as lithium, sodium, potassium, cesium, calcium, magnesium, ammonium and combinations thereof. The salts of chelating compounds may completely or only partially contain the aforementioned cations (e.g., sodium) as well as acidic protons, such as Nax(C6H8-xO7) or NaxEDTA, whereas X=1-4. Such salt combines with a copper source to produce NaCu(C6H5O7). Examples of suitable inorganic or organic acid salts include ammonium and potassium salts or organic acids, such as ammonium oxalate, ammonium citrate, ammonium succinate, monobasic potassium citrate, dibasic potassium citrate, tribasic potassium citrate, potassium tartrate, ammonium tartrate, potassium succinate, potassium oxalate, and combinations thereof. The one or more chelating compounds may also include complexed salts, such as hydrates (e.g., sodium citrate dihydrate).
- Although the plating solutions are particularly useful for plating copper, it is believed that the solutions also may be used for depositing other conductive materials, such as platinum, tungsten, titanium, cobalt, gold, silver, ruthenium and combinations thereof. A copper precursor is substituted by a precursor containing the aforementioned metal and at least one ligand, such as cobalt citrate, cobalt sulfate or cobalt phosphate.
- Wetting agents or suppressors, such as electrically resistive additives that reduce the conductivity of the plating solution may be added to the solution in a range from about 10 ppm to about 2,000 ppm, preferably in a range from about 50 ppm to about 1,000 ppm. Suppressors include polyacrylamide, polyacrylic acid polymers, polycarboxylate copolymers, polyethers or polyesters of ethylene oxide and/or propylene oxide (EO/PO), coconut diethanolamide, oleic diethanolamide, ethanolamide derivatives or combinations thereof.
- One or more pH-adjusting agents are optionally added to the plating solution to achieve a pH less than 7, preferably between about 3 and about 7, more preferably between about 4.5 and about 6.5. The amount of pH adjusting agent can vary as the concentration of the other components is varied in different formulations. Different compounds may provide different pH levels for a given concentration, for example, the composition may include between about 0.1% and about 10% by volume of a base, such as potassium hydroxide, ammonium hydroxide or combinations thereof, to provide the desired pH level. The one or more pH adjusting agents can be chosen from a class of acids including, carboxylic acids, such as acetic acid, citric acid, oxalic acid, phosphate-containing components including phosphoric acid, ammonium phosphates, potassium phosphates, inorganic acids, such as sulfuric acid, nitric acid, hydrochloric acid and combinations thereof.
- The balance or remainder of the plating solution described herein is a solvent, such as a polar solvent. Water is a preferred solvent, preferably deionized water. Organic solvents, for example, alcohols or glycols, may also be used, but are generally included in an aqueous solution.
- The plating solution may include one or more additive compounds. Additive compounds include electrolyte additives including, but not limited to, suppressors, enhancers, levelers, brighteners and stabilizers to improve the effectiveness of the plating solution for depositing metal, namely copper to the substrate surface. For example, certain additives may decrease the ionization rate of the metal atoms, thereby inhibiting the dissolution process, whereas other additives may provide a finished, shiny substrate surface. The additives may be present in the plating solution in concentrations up to about 15% by weight or volume, and may vary based upon the desired result after plating.
- In one embodiment, a plating solution includes at least one copper source compound, at least one chelating or complexing compound and solvent. In one aspect the at least one copper source compound includes copper sulfate, the chelating compound includes citrate salt and the solvent is deionized Water. Copper sulfate is dissolved in deionized water to produce a copper sulfate solution with a concentration of about 0.25 M. Similarly, sodium citrate dihydrate is dissolved in deionized water to solution with a concentration of about 0.5 M. The two aforementioned solutions are combined to form a plating solution with a pH in the range from about 5 to about 6. In another aspect, the copper source (e.g., copper sulfate) and the chelating compound (e.g., sodium citrate dihydrate) may be combined as solids and then dissolved to the acceptable concentration with water.
- In another embodiment, a plating solution includes at least one copper source compound, at least one chelating or complexing compound, at least one wetting agent and solvent. In one aspect the at least one copper source compound includes copper sulfate, the chelating compound includes a citrate salt, the wetting agent includes copolymers of ethylene oxide and propylene oxide and the solvent is deionized water. The copper sulfate and the citrate solutions of above are combined with about 200 ppm of the copolymer (ethylene and propylene oxides) to form a plating solution with a pH in the range from about 5 to about 6.
- In another embodiment, a plating solution includes at least one copper source compound, at least one chelating or complexing compound and solvent. In one aspect the at least one copper source compound includes copper sulfate, the chelating compound includes boric acid and the solvent is deionized water. Copper sulfate is dissolved in boric acid to form a plating solution with a pH in the range from about 5 to about 6. The copper sulfate has a concentration of about 0.25 M and the boric acid has a concentration of about 0.40 M.
- In another embodiment, a plating solution includes at least one copper source compound, at least one chelating or complexing compound, at least one wetting agent and solvent. In one aspect the at least one copper source compound includes copper sulfate, the chelating compound includes a citrate salt, the wetting agent includes copolymers of ethylene oxide and propylene oxide and the solvent is deionized water. The copper sulfate and the citrate solutions of above are combined with the copolymer (ethylene and propylene oxides) to form a plating solution with a pH in the range from about 5 to about 6.
- The copper seed is deposited using any of the aforementioned plating solutions within a cell on the Electra Cu ECP® system or the SlimCell Copper Plating system, both of which are available from Applied Materials, Inc. of Santa Clara, Calif. The plating cells of these systems, or other plating systems utilized, may be modified to allow a more uniform electric field than produced from the standard cell. One adjustment includes the replacement of the solid anode with a segmented anode. In another aspect, a shutter or shield is added to the cell to direct current in a more uniform field about the substrate surface.
- The substrate surface, containing a barrier layer, is exposed to a plating solution. A bias commences from the anode, on the bottom of the cell, through the plating solution and across the substrate surface. The voltage is generally kept constant though the process at a range from about −0.9 V to about −0.3 V, such that the current density across the substrate surface is about 10 mA/cm2 or less, preferably about 3 mA/cm2 or less. The copper seed layer is deposited as the voltage or current reduces the complexed copper ions within the plating solution. The copper seed layer is deposited to a thickness in a range from about 50 Å to about 300 Å. In one aspect, the thickness is about 300 Å or less, preferably at about 200 Å or less and more preferably, at about 100 Å or less.
- After the copper seed layer is deposited, the substrate is rinsed to eliminate contamination of subsequent plating solutions by the copper plating solution. The substrate is rinsed with an aqueous solution, preferably deionized water, for a period from about 5 seconds to about 30 seconds, while rotating at a rate from about 20 rpm to about 400 rpm. Subsequently, the substrate is dried via gas flow, such as nitrogen, argon, helium, hydrogen or combinations thereof.
- Following the rinse/dry step, the substrate is annealed, preferably thermally annealed in an environment containing hydrogen gas, to obtain a better crystal orientation. Better crystal orientations improve electromigration resistance of the subsequent copper migration. The substrate is placed into a rapid thermal process (RTP) chamber, such as the RTP XEplus Centura® or the anneal chamber of the Electra iECP® or SlimCell plating systems, both of which are available from Applied Materials, Inc. of Santa Clara, Calif. The chamber is generally an oxygen-free environment, usually containing a gas, such as nitrogen, argon, helium, hydrogen or combinations thereof. The substrate is annealed for a period in the range from about 5 seconds to about 180 seconds at a temperature in the range from about 150° C. to about 350° C. The annealing duration may also be between about 5 seconds and about 20 seconds.
- After the annealing step, a second copper deposition step, a gap-fill step, is carried out. The gap-fill step includes a solution containing about 0.05-0.5 M H2SO4, about 20-100 ppm level of CI, about 8-24 ppm SPS (an accelerator), about 50-500 ppm co-polymer of ethylene oxide and propylene oxide (EO/PO co-polymer as wetting agents) and less than about 100 ppm polyamine as a leveler.
- Subsequently, a second annealing step is performed, followed by a third copper deposition step, which is a bulk-fill step. The bulk-fill step includes a deposition solution that was made by adding at least one leveling agent (e.g., polyamine or polyimidazole) to the solution used during the gap-fill deposition. The leveling agent is used to achieve a better planarization. Also, pulsed, reversed current can be introduced to fine-tune the planarity of the final copper deposition.
- The following non-limiting examples are provided to further illustrate embodiments of the invention. However, the examples are not intended to be all inclusive and are not intended to limit the scope of the invention described herein.
- A copper seed layer was deposited onto a substrate containing a barrier layer (cobalt). The copper seed was deposited using the following plating solution within a modified cell on the Electra Cu ECP® system. A substrate was disposed in a basin containing a plating solution of:
- about 0.25 M copper sulfate in deionized water; and
- about 0.5 M sodium citrate dihydrate in deionized water.
- Therefore, the plating solution had a pH of about 6. Electricity was applied at a current density of about 2 mA/cm2. The plating process continued until the seed layer was deposited to a thickness of about 100 Å.
- The substrate was rinsed in deionized water for about 30 seconds while rotating at about 100 rpm and then dried via an argon gas flow. The substrate was annealed in an O2-free environment for 30 seconds, in the annealing chamber of the Electra iECP system.
- After the annealing step, a gap-fill deposition step, is carried out. The gap-fill step includes a solution containing CuSO4 (0.25 M), H2SO4 (0.3 M), 50 ppm level of CI, 15 ppm SPS (an accelerator), 200 ppm of EO/PO co-polymer of mean molecular weight of 5,000.
- Subsequently, another annealing step is performed followed by a bulk-fill deposition step. The bulk-fill step includes a deposition solution made by adding polyamine (a leveling agent) to the solution used during the gap-fill.
- A copper seed layer was deposited onto a substrate containing a barrier layer (cobalt). The copper seed was deposited using the following plating solution within a modified cell on the Electra Cu ECP® system. A substrate was disposed in a basin containing a plating solution of:
- about 0.25 M copper sulfate in deionized water;
- about 0.5 M sodium citrate dihydrate in deionized water; and
- about 200 ppm of polycarboxylate (EO/PO) copolymers.
- The plating solution had a pH of about 5.8. Electricity was applied at a current density of about 2.0 mA/cm2. The plating process continued until the seed layer was deposited to a thickness of about 100 Å.
- A copper seed layer was deposited onto a substrate containing a barrier layer (ruthenium). The copper seed was deposited using the following plating solution within a modified cell on the Electra Cu ECP® system. A substrate was disposed in a basin containing a plating solution of:
- about 0.3 M copper sulfate in deionized water; and
- about 0.5 M boric acid in deionized water.
- The plating solution had a pH of about 5. Electricity was applied at a current density of about 2.0 mA/cm2. The plating process continued until the seed layer was deposited to a thickness of about 100 Å.
- A copper seed layer was deposited onto a substrate containing a barrier layer (ruthenium). The copper seed was deposited using the following plating solution within a modified cell on the Electra Cu ECP® system. A substrate was disposed in a basin containing a plating solution of:
- about 0.3 M copper citrate in deionized water;
- about 0.5 M boric acid in deionized water; and
- about 200 ppm EO/PO co-polymer.
- The plating solution had a pH of about 5. Electricity was applied at a current density of about 2.0 mA/cm2. The plating process continued until the seed layer was deposited to a thickness of about 100 Å.
- A copper seed layer was deposited onto several substrates containing a cobalt barrier layer consistent to the procedure of Example 1. The substrates were examined by various means upon commencing the plating process with a seed layer thickness of about 100 Å. A tape test determined strong adhesion existed between the barrier layer and the copper seed layer. The conductivity of the copper seed layer was qualitatively high. Furthermore, little or no oxidation occurred to the barrier layer during the deposition of the seed layer.
- While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (18)
1. A method for depositing a copper-containing seed layer onto a barrier layer, comprising:
providing a substrate comprising the barrier layer disposed on a substrate surface, wherein the barrier layer has a barrier surface selected from the group consisting of a tungsten surface, a tungsten nitride surface, a titanium surface, a titanium nitride surface, a cobalt surface, a ruthenium surface, a nickel surface, and a silver surface; and
exposing the substrate to a first electroplating solution comprising complexed copper ions that have more negative deposition potential relative to free copper ions to deposit a copper seed layer directly on the barrier layer.
2. The method of claim 1 , wherein the electroplating solution has a pH value of less than 7.
3. The method of claim 1 , wherein exposing the substrate further comprises:
applying a first electrical bias across the substrate surface to deposit the copper seed layer on the barrier layer.
4. The method of claim 1 , wherein the complexed copper ions are derived from a copper source selected from the group consisting of copper citrate, copper borate, copper tartrate, copper oxalate, derivates thereof, and combinations thereof.
5. The method of claim 1 further comprising:
applying a second electrical bias across the substrate surface to deposit a copper gap-fill layer onto the copper seed layer.
6. The method of claim 5 , further comprising depositing a copper bulk-fill layer by:
applying a third electrical bias across the substrate surface to deposit the copper bulk-fill layer onto the copper gap-fill layer.
7. The method of claim 3 , wherein the first electrical bias has a current density of less than about 10 mA/cm2 across the substrate surface.
8. The method of claim 1 , wherein the copper source is copper citrate.
9. The method of claim 1 , wherein the first electroplating solution contains a copper concentration within a range from about 0.02 M to about 0.8 M.
10. The method of claim 1 , wherein the copper seed layer has a thickness of less than about 200 Å.
11. The method of claim 1 , wherein the barrier layer consists essentially of cobalt, ruthenium, nickel, or tungsten.
12. The method of claim 3 , wherein the complexed copper ions in the electroplating solution chemically reduce complexed copper ions with the first electrical bias to form the copper seed layer on the barrier surface.
13. The method of claim 1 , wherein the barrier layer is a ruthenium barrier layer.
14. The method of claim 1 , wherein the copper seed layer is directly formed on the barrier surface without intervening layer disposed therebetween.
15. The method of claim 6 , further comprising:
annealing the copper gap-fill layer.
16. The method of claim 1 , wherein the complexed copper solution has a pH value within a range from about 4.5 to about 6.5.
17. The method of claim 1 , wherein the first electrical bias has a current density within a range from about 0.5 mA/cm2 to about 3 mA/cm2 across the substrate surface.
18. The method of claim 15 , further comprising:
annealing the copper gap-fill layer in an oxygen free environment.
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Also Published As
Publication number | Publication date |
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TW200506107A (en) | 2005-02-16 |
EP1649502A1 (en) | 2006-04-26 |
JP4771945B2 (en) | 2011-09-14 |
JP2007528932A (en) | 2007-10-18 |
US20050006245A1 (en) | 2005-01-13 |
WO2005008759A1 (en) | 2005-01-27 |
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